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JOURNAL OF MOLECULAR LIQUIDS · 2019 · IF 4.561

Removal of Cu(II) from wastewater using doped HAP-coated-limestone

Xilong Peng,Wenjin Chen,Zongjian He,Dan Li,Heng Liu,Hong Jin,Guigen Zhou,Feigao Xu

Reducing copper content in copper-containing water is a worldwide environmental problem. It has been shown that hydroxyapatite (HAP) has a significant adsorption effect on heavy metals (including Cu 2+ ). In this study, doped HAP-coated-limestone was synthesized using waste limestone, diammonium hydrogen phosphate and two kinds of chloride (Mg 2+ , Sr 2+ ). The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrophotometry (FTIR), thermogravimetric analysis (TGA), Brunner-Emmet-Teller (BET) measurements and scanning electron microscope (SEM). It was found that the structure of Mg 2+ and Sr 2+ doped HAP-coated-limestone was similar to that of HAP-coated-limestone. The surface of doped HAP-coated-limestone is rougher, and the specific surface area is larger than that of HAP-coated-limestone. Some factors have been investigated affecting the uptake behavior, such as doped element, contact time, temperature and Cu 2+ concentration to optimize the conditions. The adsorption isotherms of Langmuir and Freundlich were studied, and it was proved that the adsorption isotherm of Langmuir was more consistent with the adsorption process of doped HAP-coated-limestone. The quasi-second-order dynamics can be better used to describe the experimental results compared with quasi-first-order dynamics. At the temperature of 30 °C, the adsorption capacity of HAP-coated-limestone for Cu (II) is 90.90 mg·g −1 , while the adsorption capacity is 214.20 and 121.61 mg·g −1 for Mg 2+ and Sr 2+ doped HAP-coated-limestone, respectively. Through the calculation of thermodynamic parameters, the results show that the adsorption process of Cu (II) on HAP-coated-limestone and doped HAP-coated-limestone becomes easier with the increase of temperature in a certain temperature range. The adsorption process on HAP-coated-limestone and doped HAP-coated-limestone is spontaneous and endothermic.

研究领域: 环境科学 · 材料科学
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2018 ·Vol. 25 ·期 16 ·15492-15506 · IF 2.8

Effect of Cu(II) on the stability of oxyanion-substituted schwertmannite

Li Junfei,Xie Yingying,Lu Guining,Ye Han,Yi Xiaoyun,Reinfelder John R.,Lin Zhang,Dang Zhi

Schwertmannite, a Fe(III)-oxyhydroxysulfate mineral formed in acidic (pH 3~4), iron- and sulfate-rich acid mine drainage (AMD) environments, tends to undergo phase transformations with changes in pH and redox condition, which may depend on the presence of various trace anions and cations. In the present study, the effects of Cu(II) on the stability of arsenate-, chromate-, and molybdate-substituted schwertmannite were investigated. The release of Fe(III) and sulfate from schwertmannite seems to be accelerated in the presence of Cu(II) at pH ~ 3, while Cu(II) retarded the dissolution of schwertmannite at pH ~ 5. XRD and SEM results showed that pure schwertmannite and chromate-substituted schwertmannite underwent transformation to goethite over a 2-month period, the presence of Cu(II) enhanced the stability of the mineral’s structure at both pH 3 and 5. However, the structures of arsenate- and molybdate-substituted schwertmannites showed no significant changes in the presence or absence of Cu(II) at both pH 3 and 5. During the phase transformation process, the amount of released oxyanions followed the sequence of chromate > molybdate > arsenate. Moreover, the release of arsenate and chromate from schwertmannite was retarded in the presence of Cu(II) at pH 5, whereas the release of molybdate was promoted. These results have important environmental implications for the stability of schwertmannite and its potential to immobilize contaminant trace elements under AMD conditions.

研究领域: 环境科学 · 矿物学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Rapid acceleration of Cu(II)/peroxymonosulfate oxidation of phosphonate by hydroxylamine

Jinglin Zhu,Yutao Huang,Juanjuan Peng,Shaomin Liu

Developing simple and effective activation approaches to degrade phosphonate is crucial due to its potential aquatic environmental risks. Recently, Cu(II)-mediated activation processes provide a feasible method via nonradical oxidation mechanism to remove phosphonate, but is yet challenged under neutral conditions. Herein, a strategy for enhancing the Cu(II)/peroxymonosulfate (PMS) process by adding hydroxylamine (HA) could efficiently degrade 1-hydroxyethane1,1-diphosphonic acid (HEDP) at pH = 7.0. After 15-min reaction, 85.7% of total phosphorus (TP) in HEDP transformed into PO 4 3− in the Cu(II)/PMS/HA process is observed, which is 3.4 times than that in the Cu(II)/PMS process. The results of multiple experiments confirm that the presence of HA accelerates the reduction of Cu(II) and the generation of reactive species, SO 4 •− and Cu(III) induced intramolecular electron transfer as the primary reactive species play a significant role in the degradation of HEDP. Additionally, the removal of HEDP is inhibited with the addition of Cl − and HCO 3 − in the Cu(II)/PMS/HA process. However, the Cu(II)/PMS/HA process demonstrates a superior removal effectiveness of HEDP in different actual wastewater samples compared to the Cu(II)/PMS process under neutral conditions. This study provides an effective method for removing phosphonate from actual wastewater.

研究领域: 环境科学 · 水处理工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Mechanisms of Cu(II) enhancing photolysis of tetracycline under UV irradiation

Chang Xu,Yue Feng,Xin-Xin Zhao,Shan Zhao,Shu-Guang Wang,Chao Song

Tetracycline (TC) and Cu(II) have been frequently detected in natural and engineering waters, especially in aquaculture water. However, literatures involving in the influence of Cu(II) on the transformation of TC are still insufficient. In this study, we investigated the photolytic fate of TC induced by Cu(II) under UV irradiation. Cu(II) significantly promoted the removal of TC with photolysis rate constant of 0.467 h −1 at TC:Cu(II) molar ratio = 1, which was 49.04% higher than that without Cu(II) (0.238 h −1 ). Cu(II) exhibited multiple influences on both direct and indirect photolysis of TC. Singlet oxygen ( 1 O 2 ) and hydroxyl radicals (·OH) made a major contribution to Cu(II)-induced TC photolysis, with contribution rates of 24.69% and 12.96%, respectively. Besides, Cu(II) preferred to complex between O20-O21 or O26-O27 to form TC-Cu(II) complexes with complexation ratio of 1. The Condensed Fukui Function and Condensed Double Descriptors values of TC-Cu(II) complexes were calculated for the first time with density functional theory. It showed that TC-Cu(II) complexes were more vulnerable to ROS attack, thus promoting TC degradation. Moreover, Cu(II) greatly changed the photolysis path of TC, mainly through hydroxylation, hydrogen extraction, and deamidation reaction into new byproducts. Furthermore, Cu(II) changed the toxicity of the products via changing the original TC photolysis products. This study provides new insights for the environmental fate of antibiotics, and also has far-reaching implications for wastewater treatment in pharmaceutical and aquaculture industry.

CAS / MDL: 60-54-8
研究领域: 环境科学 · 水处理工程
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MICROCHIMICA ACTA · 2017 ·Vol. 184 ·期 9 ·3121-3130 · IF 4.58

Voltammetric hybridization assay for the β1-adrenergic receptor gene (ADRB1), a marker for hypertension, by using a metal organic framework (Fe-MIL-88NH2) with immobilized copper(II) ions

Yuan Guolin,Wang Lei,Mao Dayong,Wang Fang,Zhang Jicai

The β1 receptor blocker metoprolol targets the hypertension-carrying adrenergic receptor gene (ADRB1), but therapy is often hindered by a lack of evidence-based medical information. The authors describe an assay for the ADRB1 gene. It is based on the electrocatalytic oxidation of H 2 O 2 by a nanocomposite consisting of hemin and platinum nanoparticles in an amino-modified metal-organic framework of the type Fe-MIL-88-NH 2 and heavily loaded with Cu(II) ions. The nanocomposite was placed on a glassy carbon electrode (GCE), and the resulting sensor displays increased electrocatalytic activity with the addition of H 2 O 2 because of the synergistic effects of hemin and the platinum nanoparticles (Pt NPs). Next, a capture DNA probe for the target ADRB1 gene was immobilized on the modified GCE. Binding of the target gene results in a distinct change in the electrocatalytic activity of H 2 O 2 . The amperometric i–t curves were recorded at −0.4 V in 5 mL of phosphate buffered saline at room temperature. The electrode responds to ADRB1 in the 1 f. to 10 nM concentration range and has a 0.21 f. detection limit (at a S/N ratio of 3). In our perception, this detection scheme can simplify and accelerate the identification of drug response and therapeutic efficacy. Conceivably, it may be applied to other mutations, and it may enable a more precise clinical prognosis and thus facilitate personalized medical diagnostics. Schematic presentation of an electrode for the determination of the adrenergic receptor gene (ADRB1). The assay is based on the electrooxidation of added H 2 O 2 by using a glassy carbon electrode (GCE) coated with a composite prepared from platinum nanoparticles (Pt NPs), hemin and a metal-organic framewok of type Fe-MIL-88NH 2 loaded with Cu(II). This versatile platform simplifies studies on the response of hypertension drugs and the effectiveness of therapy.

研究领域: 生物化学 · 医学诊断 · 纳米材料科学
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Advanced Healthcare Materials · 2025 · IF 9.6

Shikonin-Cu(II) Supramolecular Polymers Exhibit Antitumor Activity via Necrosis and Cuproptosis

Hongyang Zhang,Rui-Hong Gong,Yu−Shan Lin,Tao Wang,Dou Luo,Jiahua Li,Li-Sha Shen,Wai-Yeung Wong,Sibao Chen,Guo-Qing Chen

Supramolecular polymers driven by the metal-ligand coordination possess reversible bonds, making them promising candidates for integrating the therapeutic functions of metal ions and small-molecule drugs, and subsequently releasing these components within cells after endocytosis. In this study, a kind of supramolecular polymer, SHICU, is developed, composed of Shikonin ligand and Cu(II) ion. Upon reduction by intracellular glutathione (GSH), SHICU dissociates to release Shikonin, Cu(II), and SHICU fragments. The released Shikonin and Cu(II) exhibit a synergistic antitumor effect through the reactive oxygen species (ROS)-dependent necrosis. Meanwhile, the released SHICU that remains structural integrity induces a distinct antitumor mechanism by triggering cuproptosis in tumor cells. This dual functionality, combining ROS-dependent necrosis and cuproptosis, highlights the potential of SHICU in advancing antitumor therapies, while the integration of supramolecular polymers with the emerging cell death mechanism of cuproptosis facilitates the development of innovative cancer drugs.

CAS / MDL: 10125-13-0
研究领域: 药理学 · 肿瘤学 · 生物化学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Organically-coordinated Cu(II) mediated AOPs: A comparative study on different peroxides

Mengyao Shi,Qiang Yin,Da Wang,Chengcheng Tian,Lei Zhou

The widespread presence of Cu(II) in aquatic environment has attracked increasing interests in Cu(II)-mediated advanced oxidation processes (AOPs) as a promising “two-birds-one-stone” strategies for environmental remediation. Organically coordinated Cu(II) systems offer dual benefits on facilitating efficient copper redox cycling and generating reactive species for pollutant degradation. However, the activation efficiency disparities among different peroxides and their underlying mechanisms remain poorly understood. Herein, this study presents a comprehensive comparison of organically-cooridinated Cu(II) activated peroxydisulfate (PDS), peroxymonosulfate (PMS) and hydrogen peroxide (H 2 O 2 ) systems, where ofloxacin (OFX) serving as coordinating ligand and target contaminant. Our results demonstrate enhanced activation for all the three peroxides, leading to significantly improved OFX degradation. High-valent copper species Cu(III) is identified as the primary working intermediate across all systems. The peroxides activation efficiency, OFX decay enhancement, and steady-state Cu(III) concentration consistently followed an order of PDS > H 2 O 2  > PMS. The performance differences among the three systems were governed by the initial contact probability between peroxides and copper center and the subsequent electron transfer efficiency, which is further verified by molecular dynamics (MD) simulations. This work establishes a quantitative framework for predicting peroxides activation properties in Cu(II)-mediated AOPs, offering fundamental insights for designing efficient dual-functional systems that combine heavy metal stabilization with organic pollutant degradation in wastewater treatment.

研究领域: 环境化学 · 高级氧化过程 · 水处理 · 污染物降解 · 金属-有机相互作用
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RSC Advances · 2020 ·Vol. 10 ·期 35 ·20504-20514 · IF 3.119

Aqueous Cu(II) ion adsorption by amino-functionalized mesoporous silica KIT-6

Jianwen Wei,Siqi Chen,Yu Li,Zeyu He,Linlin Geng,Lei Liao

To find an alternative adsorbent with high adsorption performance, KIT-6 was prepared by hydrothermal crystallization synthesis using tetraethyl orthosilicate as a silicon source and triblock copolymer P123 as a template. Then the silane coupling agent (3-chloropropyl)trimethoxysilane was first grafted onto KIT-6 mesoporous material and then the polyethyleneimine (PEI) was further grafted through the substitution reaction between amino groups and chlorine atoms. The functionalized KIT-6 was denoted as PEI/KIT-6. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption–desorption, elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA). The Cu2+ adsorption performance was determined by inductively coupled plasma (ICP). The results showed that the average loading of the amino groups was 3.74 mmol g−1, and the modified KIT-6 still has a stable mesoporous structure without pore blockage. With the dosage of 1 g L−1 PEI/KIT-6 and at room temperature, the optimum pH value for adsorption of 100 mg L−1 Cu2+ was 6.0. The adsorption capacity of PEI/KIT-6 for Cu2+ increased with the increase of reaction temperature, and the maximum adsorption capacity of Cu2+ was 36.43 mg g−1. The adsorption capacity tends to reach equilibrium after 120 min, and the optimum adsorption temperature was 35 °C. The pseudo-second-order kinetic model was found to be well suited for the adsorption process of Cu2+. Adsorption equilibrium data could also be described well by the classical Langmuir and Freundlich isotherm models. The adsorption tends to be the chemisorption of a monolayer.

研究领域: 材料科学 · 环境科学
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2018 · IF 3.862

A multifunctional ternary Cu(II)-carboxylate coordination polymeric nanocomplex for cancer thermochemotherapy

Cuiting Zhang,Jing Li,Chenggen Qian,Xinping Luo,Kaikai Wang,Peixuan Zhao,Minjie Sun

Metal-based photothermal therapy has been widely used in the biomedicine field and includes gold nanoparticles , silver nanoparticles and copper sulfide nanoparticles. Furthermore, the coordination bonding-based metal nanocomplex is a new generation of photothermal agents for cancer therapy due to its high photothermal transduction efficiency, good biocompatibility , biodegradation and bioactivity. In this study, we designed a coordination bonding-based copper (Cu(II))-carboxylate ternary architecture, which consists of a conjugate dopamine-modified nontoxic hyaluronic acid , copper ions and citric acid. When the Cu(II) coordinated with the carboxyl groups , the splitting d orbitals energy gap of Cu(II) and the capability of electron transition were enhanced, which can increase the extinction ability in the near-infrared region for enhancing photothermal therapy. Moreover, the degradation of hyaluronic acid by hyaluronidase highly expressed in the tumor microenvironment led to the release of Cu-citric acid complexes, thus exhibiting an additional chemotherapeutic effect. The nanocomplexes possessed high-performance photothermal conversion, determined to be 21.3%. The solution could be easily heated to above 42 °C, which was sufficient to ablate the cancer cells. An obvious decrease in cell viability was observed in B16F10 cells incubated with the nanocomplexes under laser at the lower concentration of 20 μg/mL Cu(II). Upon near-infrared laser irradiation, the nanocomplexes showed high photothermal therapy and chemotherapeutic efficacy for breast cancer in vivo . This study demonstrated that the Cu(II)-carboxylate coordination nanocomplex is a promising new effective and facilely prepared thermochemotherapy agent for combination therapy against cancer.

研究领域: 生物医学 · 纳米医学 · 癌症治疗
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JOURNAL OF SOLID STATE CHEMISTRY · 2021 · IF 3.498

Removal of Cu (II) from aqueous solutions using ZIF-8@GO composites

Dan Li,Feigao Xu

ZIF-8@GO-X (X ​= ​0, 2.48%, 4.07%, 7.83%, and 20.03%) composites were prepared using GO and ZIF-8. The composites were used to absorb Cu(Ⅱ) from aqueous solutions. With increasing GO content, the adsorption of the ZIF-8@GO-X composites first increased and then decreased. The Cu(Ⅱ) adsorption of ZIF-8@GO-7.83% reaches a maximum among ZIF-8@GO-X composites (X ​= ​0, 2.48%, 4.07%, 7.83%, and 20.03%). The adsorption kinetics , adsorption isotherm , adsorption thermodynamics, and adsorption mechanism of Cu (II) by ZIF-8@GO-7.83% were studied in this paper. The results showed that the adsorption reached equilibrium at 120 ​min, and ZIF-8@GO-7.83% approached equilibrium relatively quickly. When the temperature was 45 ​°C and the Cu(Ⅱ) concentration was 40 ​mg/L, the maximum adsorption capacity of ZIF-8@GO-7.83% for Cu(Ⅱ) reached 482.29 ​mg/g. The equilibrium data and kinetics were well described by Langmuir and pseudo-first-order models, respectively. Final experiments with real factory wastewater (initial Cu(Ⅱ) concentration of 670 ​mg/L) revealed that 0.37 ​g/L ZIF-8@GO-7.83% can efficiently reduce the Cu(Ⅱ) concentration to below 2 ​mg/L.

研究领域: 环境科学 · 材料科学
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JOURNAL OF HAZARDOUS MATERIALS · 2019 · IF 7.65

Preparation and characterization of amino/thiol bifunctionalized magnetic nanoadsorbent and its application in rapid removal of Pb (II) from aqueous system

Jiujiang Ji,Guo Chen,Jun Zhao

To explore the effect of coexisted amino and thiol groups on adsorption of heavy metal, a novel magnetic nanoparticle was prepared by sequentially modification with (3-Chloropropyl) trimethoxysilan, polyetherimide, epichlorohydrin and thiourea. Subsequently, it was characterized by TEM, N 2 adsorption/desorption, FTIR Spectroscopy, zeta potential, and VSM. The maximum adsorption capacity for Pb 2+ , Cd 2+ and Cu 2+ reached 110.13 mg·g −1 , 40.23 mg·g −1 and 29.37 mg·g −1 , respectively. The adsorption of the magnetic nanoparticles with different surface group for heavy metals were compared, which indicated that the amino and thiol group played an important role in the adsorption of heavy metals. Especially, the adsorption capacity increased dramatically after modification with the thiol group, which was attributed to the synergistic coordination of −NH 2 and −SH. The adsorption kinetics is consistent with the quasi-second-order kinetics equation, and the adsorption thermodynamic process is consistent with the Langmuir isotherm equation. The effects of experimental conditions, such as pH, the concentration of metals, adsorption time and temperature, on adsorption of Pb 2+ were studied in detail. In addition, over 90% of removal rate was remained after 6 cycles. The magnetic nanoadsorbents was a promising nanoadsorbent with high adsorption speed, simultaneous adsorption of various heavy metals, strong anti-interference ability and reusability.

CAS / MDL: 123-99-9 9002-98-6
研究领域: 环境科学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

The catalytic role of nascent Cu(OH)2 particles in the sulfite-induced oxidation of organic contaminants

Tao Luo,Yanan Yuan,Danna Zhou,Liting Luo,Jinjun Li,Feng Wu

In the recent years, sulfite-induced oxidation of various contaminants using oxysulfur radicals (SO 4 − , SO 5 − and SO 3 − ) has been explored to establish novel advanced oxidation processes (AOPs). Although transition metals, such as cupric ions (Cu(II)), have been demonstrated to be capable of activating sulfite (S(IV)), the catalytic mechanism of the specific Cu(II) species is still not very clear. In this work, N-acetyl- para -aminophenol (APAP) was used as a basic substrate to investigate the process, mechanism and stability of the Cu(II)-S(IV) system with low dosages of Cu(II) (0.010 mmol L −1 ) in an alkaline solution (pH 10). The results show that 0.010 mmol L −1 Cu(II) can efficiently activate S(IV) for the oxidation of APAP and other contaminants (e.g., metoprolol, sulfanilamide, aniline, 4-chloroaniline, N,N-dimethylaniline, p -nitrophenol and 3-nitrophenol). Simulation calculations for the distribution of the Cu(II) species and pH-dependence of APAP oxidation in the Cu(II)-S(IV) system showed that Cu(OH) 2 particles are the major active species in the catalysis of S(IV). The surface complexation of S(IV) with the Cu(OH) 2 particles prior to the production of oxysulfur radicals is the basic mechanism of the alkaline Cu(II)-S(IV) system. Radical inhibition with scavengers (ethanol, tert-butyl alcohol or aniline) demonstrates that SO 5 − , SO 4 − and hydroxyl radicals (HO ) are responsible for the contaminant oxidation. Moreover, SO 5 − is believed to be the main active species in the Cu(II)-S(IV) system, which has a second-order rate constant of 2.98 × 10 8  M −1  s −1 with APAP. This work renews our recognition of the Cu(II)-S(IV) system applications and further understanding of the catalytic role of the nascent Cu(OH) 2 particles in the activation of S(IV).

研究领域: 环境科学 · 化学
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