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ANALYTICAL CHEMISTRY · 2018 · IF 6.042

Self-Assembled Binuclear Cu(II)–Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry

Xiangying Yu,Man-Chu Chau,Wai Kit Tang,Chi-Kit Siu,Zhong-Ping Yao

Naproxen is one of the most consumed nonsteroidal anti-inflammatory drugs and marketed as S-naproxen since R-naproxen is hepatotoxic. In this study, chiral recognition of naproxen has been investigated by tandem mass spectrometry (MS/MS). Among all diastereomeric complexes formed between naproxen and the examined chiral selectors, including cyclodextrins (α/β/γ-CD), modified phenylalanines (N-acetyl-phenylalanine, N-t-butoxycarbonyl-phenylalanine, N-9-fluorenylmethyloxycarbonyl-phenylalanine), amino acids (Trp, Phe, Tyr, His), glucose, tartaric acid, and vancomycin, a novel binuclear metal bound diastereomeric complexes [(M(II))2(S/R-naproxen)(l-His)2−3H]+ (M = Cu, Ni, or Co with Cu being the best) could allow effective identification of the absolute configuration of naproxen and determination of its enantiomeric excess (ee) through MS/MS analysis. The key candidate structure of [(Cu(II))2(S/R-naproxen)(l-His)2−3H]+ has been revealed by means of collision-induced dissociation, ion mobility mass spectrometry and density functional theory calculations, indicating an interesting and unusual self-assembled compact geometry with the two Cu(II) ions bridged closely together (Cu–Cu distance is 3.04 Å) by the carboxylate groups of the two histidines. It was shown that the difference in dissociation efficiency between the two diastereomers was attributed to the interaction between the NH2 bond of the amino group of one histidine and the naphthyl ring of naproxen. The present report is the first to observe and characterize the complex of (Cu(II))2(His)2 with aromatic acid, which could contribute to the chiral recognition of other chiral aromatic acids, design of catalysts based on binuclear copper bound complex, as well as the better understanding of metal ion complexation by His or His-containing ligands.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Cu(II) coordination MOF-303 based dual-functional sensor for precisely detecting and distinguishing humidity and temperature with multifunction applications

Ke Wu,Lulu Guo,Wei Wang,Zhimin Yang,Haishun Liu

Humidity-temperature dual-functional sensors show great demand in healthcare and archaeology, requiring sensors with high sensitivity, high resolution and high stability. In this work, utilizing the post-coordination strategy, the uncoordinated N atoms in MOF-303 were used as the metal chelate sites to chelate CuCl 2 , and due to the accordion-like morphology, the obtained material shows potential in humidity sensing and temperature sensing. The CuCl 2 -MOF-303 based sensor shows whole range humidity sensing with response of 11.4 at 33 % RH and 56,700 at 95 % RH, 1 % RH of resolution and good long-term stability (>90 days), and excellent temperature sensing performance of high sensitivity (–3.3 %/°C), high linearity (R 2 >0.99) and high resolution (0.3 °C) in the temperature range of 35–38 °C. Furthermore, the application of sensor in healthcare, noncontact sensing and information transmission is verified. This study provides a preliminary exploration for the application of MOFs in humidity-temperature dual-functional sensors.

✓ 已验证 产品关联 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Ratiometric electrochemical biosensor based on Cu(II) modified covalent organic framework for the ultra-sensitive and specific detection of glutathione

Zeyun Yang,Hao Guo,Zhiguo Yu,Mingyue Wang,Xiaoqin Wei,Zongyan Lu,Lei Sun,Henglong Ren,Wu Yang

As a vital biological polypeptide molecule, glutathione (GSH) is involved in the regulation of various life activities. Accurate and sensitive detection of GSH in human body is of great significance for the preliminary diagnosis of related diseases. In this research, Cu(II) modified TADH COF, which has been prepared by Cu 2+ post-synthesis modification of the COF obtained through a condensation reaction of 1,3,5-(4-aminophenyl) benzene (TAPB) and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde (DHTP), and methylene blue (MB) molecules are combined to construct a ratiometric electrochemical sensor for achieving specific and ultra-sensitive detection of GSH. As a stable and active covalent organic framework material, TADH COF possesses the special O(–OH) and N(C N) binding sites, which can load and coordinate with Cu 2+ effectively. The obtained Cu(II)-TADH COF serves as a sensitive electrode material for sensing GSH due to “extrusion effect” caused CuCl solid-state electrochemical signal degeneration by the specific binding of Cu and GSH while MB provides a stable electrical signal in the electrochemical sensing process as an internal reference for eliminating errors and making the detection results more accurate. The constructed electrochemical sensing platform Cu(II)-TADH COF/MB/GCE exhibited an ultrahigh sensitivity with a limit of detection (LOD) of 0.0093 nM (S/N = 3), wide linear range of 0.05 nM–40 μM and high accuracy. For the detection of GSH in real samples including human blood, serum and urine samples, the sensor also showed excellent sensing performance. This is the first research on ratiometric electrochemical sensing platform for the ultra-sensitive detection of glutathione based on covalent organic frameworks, which provides an original and novel strategy for the electrochemical detection of GSH with COF materials.

✓ 已验证 产品关联 DOI 高影响因子
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JOURNAL OF MOLECULAR LIQUIDS · 2024 · IF 5.3

Study on Cu(II) extraction process optimization and mechanism from acidic leaching solution using the deep eutectic solvent P507/Menthol

Jue Chen,Hexiang Zhong,Shan Zhu

In this study, the selectivity of a hydrophobic deep eutectic solvent (HDES) comprising 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (P507) and L-menthol (Men) was assessed for the extraction and separation of Cu(II), Co(II), and Ni(II) from acidic leaching solutions, aiming to make the HDES system more consummate and provide a novel approach for metal extraction using HDES. The results indicated that under the conditions of a 2:1 M ratio of P507 to Men, an extraction temperature of 40℃, an extraction time of 40 min, an oil-water ratio(O/W, v/v) of 1, and a pH value of 4, the three-stage cross-flow extraction efficiency of the HDES for Cu(II) was over 99 %. Furthermore, successful selective separation of Cu(II), Ni(II), and Co(II) was demonstrated by separation coefficients β Cu/Ni of 2150 and β Cu/Co of 305. Molecular dynamics (MD) simulations and density functional theory (DFT) indicated that the formation of an HDES molecule involved the combination of two molecules of P507 and one molecule of Men through hydrogen bonding interactions. Moreover, compared to other cupric complex configurations, the tetrahedral cupric complex, synthesized using two molecules of P507 and two molecules of menthol with Cu(II), exhibited a lower single-point energy and a higher ΔE(LUMO-HOMO), demonstrating greater stability.

✓ 已验证 产品关联 DOI 高影响因子
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JOURNAL OF FLUORESCENCE · 2025 · IF 3.1

Determination of Trace Cu(II) Ions Using a Siraitia Grosvenorii Residue-derived Nitrogen-doped Carbon Dots-enabled Fluorescence Quenching Sensor

Wu Mengying,Huang Xiyang,Li Zhouquan,Gan Xiang,Zheng Yumei,Tang Hui,Xiong Jingwei,Yang Xiaoli,Yang Dongye,Zhang Lizhen,Liang Weiyuan,Li Hongtao

Bio-based fluorescent carbon dots (CDs) have emerged as promising material for advanced sensing applications due to their exceptional sensitivity, stability and biocompatibility. However, it was till constrained by ion selectivity and solution suitability especially in physiological solutions (e.g., PBS). Herein, a novel nitrogen-doped carbon dots (N-CDs) fluorescence quenching sensor derived from Siraitia grosvenorii (named “Luo Han Guo” in China) residue was developed for selective determination of trace Cu(II) ions in different solutions. The N-CDs were synthesized through a one-step hydrothermal process utilizing agricultural waste as carbon precursor and urea as the nitrogen source, demonstrating an eco-friendly synthesis strategy. The developed sensor exhibited remarkable anti-interference capability against acid, base, salt and various metal ions while maintaining excellent photostability and biocompatibility (cell viability > 75% at 1000 ug/mL). With a limit of detection (LOD) of 0.13 µmol/L, the system showed superior sensitivity compared to conventional methods. Furthermore, the sensor demonstrated strong universality across solution types and, more importantly, suitability for trace Cu²⁺ quantification in physiological solutions. Experimental results demonstrated that the fluorescence quenching process resulted from the binding of Cu²⁺ to amino groups on CDs, forming complexes through a non-radiative photoinduced electron transfer (PET) mechanism. This PET effect synergizes with static quenching, underlying the high selectivity and sensitivity of N-CDs for Cu²⁺ detection. The integration of novel phytochemical-based sensing materials with a fluorescence quenching mechanism enables highly selective detection of trace Cu²⁺ for environmental and biomedical applications.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Revealing the contribution of Cu(II) and Cu(I) inherent in MOF-199 for efficient thiophene removal at room temperature

Mingxian Duan,Yeshuang Wang,Huiling Fan,Zhelin Su,Chao Yang,Jiawei Kou,Ju Shangguan

Thiophene (C 4 H 4 S) removal from coke oven gas is critical to its subsequent high valuable utilization but remains a challenge. MOF-199 was considered as a promising candidate for C 4 H 4 S adsorption removal owing to its nature of enriched opened Cu sites. However, the presence of mixed valence of Cu(II) and Cu(I) in MOF-199 makes it puzzling to their respective contribution to the removal of C 4 H 4 S. Herein, a series of MOF-199 with different Cu(I) contents were synthesized using different methods, including hydrothermal, solution diffusion, and ultrasonic, and their C 4 H 4 S adsorption performance were investigated. The respective contributions of Cu(II) and Cu(I) to the C 4 H 4 S removal was systematically discussed. The collected results indicated that although the samples prepared with different methods present a remarkable difference in textural characters, the latter was found to have a negligible influence on the C 4 H 4 S removal owing to MOF-199(H) affording an inferior surface area and pore volumes but performing the best C 4 H 4 S removal capacity of 53.7 mg S/g. The co-adsorption results of CH 3 SCH 3 and C 4 H 4 S indicated that the excellent performance of MOF-199(H) mainly attributed to the presence of Cu(I), which provides active sites for C 4 H 4 S adsorption through π complex coordination. Cu(II) species was also found to the C 4 H 4 S adsorption via soft-acid-base coordinated interaction, but its contribution is 8.3 mg S/g, only accounting for 15.5 %. Additionally, the adsorption of C 4 H 4 S on MOF-199(H) was found to follow the intra-particle diffusion model and the Langmuir models. Moreover, MOF-199(H) also exhibited an excellent regeneration performance due to the weak interaction between C 4 H 4 S and their opened Cu sites, the C 4 H 4 S adsorption capacity still reaches 50.6 mg S/g after three regeneration cycles, about 94 % of its initial value. The results collected in this study will provide new insights for the manipulation of performance of C 4 H 4 S adsorption on the MOF-199.

CAS / MDL: 554-95-0
✓ 已验证 产品关联 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Peroxymonosulfate activation by vacuum ultraviolet and trace copper ions: A new way to boost Cu(II)/Cu(I) redox cycle

Bin Zhang,Ziwen Han,Yanjun Xin,Yanjie Zhang,Wenqian Li,Boda Li,An Ding,Jun Ma,Xu He

Herein, vacuum ultraviolet (VUV) was introduced to enhance the activation rate of peroxymonosulfate (PMS) by copper ions for the first time. Compared with ultraviolet (UV), the redox cycle rate of Cu(II)/Cu(I) was prominently enhanced by VUV due to the combined driving effect of UV, hydrated electron and active hydrogen atoms. The accelerated Cu(II)/Cu(I) cycle in VUV/PMS/Cu(II) system led to 2.89 times higher degradation efficiency of 2,4-dichlorophenol (2,4-DCP) than that by UV/PMS/Cu(II) system. More importantly, the initial Cu(II) concentration (5 μM) in VUV/PMS/Cu(II) system was only 1/5 of the guideline value in WHO standards for drinking water, and the initial PMS concentration was also 1 order of magnitude lower than that in most PMS based systems for water treatment. Furthermore, the reaction mechanism and possible degradation pathways of 2,4-DCP were also proposed. This study verified the possibility for the utilization of trace Cu(II) in water to decompose refractory micro-pollutants by PMS activation.

✓ 已验证 DOI 高影响因子
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Desalination and Water Treatment · 2025 · IF 1

Preparation of polyethyleneimine/graphene oxide membranes and their adsorptions for Pb(II), Cu(II) and Zn(II) in mixed systems

Jingyi Chen,Xiaoxue Zhang,Junsheng Liu,Shan Jiang,Chunyu Ji,Jie Zhang

A series of novel polyethyleneimine/graphene oxide (PEI@GO) membranes were prepared and their adsorptions for heavy metal ions in mixed solutions were examined. It was found that they had good sorption performances for Pb(II), Cu(II), and Zn(II) in water. Their adsorptions for Pb(II), Cu(II), and Zn(II) obeyed the first-order kinetic modeling, dominating a physical style. Meanwhile, the fitting of intra-particle diffusion showed that Pb(II) and Cu(II) did not conform to the intra-particle diffusion stage, whereas Zn(II) did. Moreover, it was confirmed that the sorption of PEI@GO membranes for Pb(II), Cu(II), and Zn(II) followed the Langmuir isotherm modeling, and the maximal values could reach 79.6 mg/g for Pb(II), 35.01 mg/g for Cu(II), and 32.27 mg/g for Zn(II), respectively. The calculation of thermodynamic parameters indicated that these adsorptions were spontaneous and endothermic processes. Further, the investigation of PEI@GO membranes for Pb(II), Cu(II), and Zn(II) in ternary mixed systems evidenced that Zn(II) can be preferentially removed via step-by-step mode. In addition, the exploration of sorption mechanism using XPS and FTIR analyses showed that ligand interactions were involved in the adsorptive removal of Pb(II), Cu(II), and Zn(II). This study discloses that PEI@GO membranes are promising adsorbents for the removal of heavy metal ions from water.

CAS / MDL: 111-30-8 7782-42-5
✓ 已验证 产品关联 DOI 高影响因子
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 25 ·6645-6653 · IF 3.286

Carbon dots as an “on-off-on” fluorescent probe for detection of Cu(II) ion, ascorbic acid, and acid phosphatase

Ma Xin,Lin Shijun,Dang Yunfei,Dai Yu,Zhang Xiaojin,Xia Fan

Carbon dot (CD)-based fluorescent probes have been widely exploited; however, multi-component detection using CDs without tedious surface modification is always a challenging task. Here, we develop a convenient and simple CD-based “on-off-on” fluorescent probe for detection of copper(II) ion (Cu 2+ ), ascorbic acid (AA), and acid phosphatase (ACP). Cu 2+ leads to the fluorescence quenching of CDs. The limit of detection (LOD) for Cu 2+ is 2.4 μM. When AA is added into the CDs + Cu 2+ solution, Cu 2+ is reduced by AA to Cu + , causing the fluorescence recovery of CDs. The fluorescent intensity linearly correlates with the concentration of AA in the range of 100–2800 μM with LOD of 60 μM. Besides, the probe has potential application for detection of AA in real samples such as VC tablets, orange juice, and fresh orange. The probe can also indirectly detect ACP that enzymatically hydrolyzes ascorbic acid-phosphate (AAP) to produce AA. This work expands the application of CDs in the multi-component detection and provides a facile fluorescent probe for detection of AA in real samples. Graphical abstract

✓ 已验证 DOI PubMed 高影响因子
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2021 · IF 5.268

Fabrication of in situ ZIF-67 grown on alginate hydrogels and its application for enhancing Cu (II) adsorption from aqueous solutions

Zhiyue Li,Zhiwei Guo,Taoyi Zhang,Quan Li,Jing Chen,Wenxi Ji,Cong Liu,Yun Wei

Synthesizing high uniform metal-organic frameworks grown on natural biomass such as sodium alginate (ALG), which can efficiently remove metal ions from aqueous solution, is a challenging project. A simple and eco-friendly method of preparing ALG@ZIF-67 hydrogels by in situ synthesis of ZIF-67 onto ALG hydrogels was established. Combining the virtues of ALG with abundant hydroxyl and carboxyl groups and ZIF-67 with excellent porous structure, the obtained ALG@ZIF-67 hydrogels have excellent adsorption for Cu 2+ (153.63 mg/g), which was much higher than that of pure ALG hydrogels (111.79 mg/g). The methodology showed that the adsorption process was in accord with the Langmuir isotherm adsorption model (R 2 = 0.9972) and pseudo-second-order kinetic model (R 2 = 0.9822). The thermodynamic experiments demonstrated that Cu (II) was absorbed by hydrogel with an endothermic and spontaneous process. The competitive adsorption experiment results of ALG@ZIF-67 hydrogel indicated that the absorption capacity of Cu (II) was higher than that of Cd (II), Ni (II), Zn (II) and Mn (II). Moreover, the ALG@ZIF-67 hydrogels still had excellent reusability after five adsorption-desorption cycles. The results indicated that the ALG@ZIF-67 hydrogels had the advantages of low cost, easy preparation, and environment friendly.

研究领域: 环境科学 · 材料科学
✓ 已验证 DOI 高影响因子
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Polymers · 2016 ·Vol. 8 ·期 4 ·78 · IF 2.944

Preparation of Highly Dispersed Reduced Graphene Oxide Modified with Carboxymethyl Chitosan for Highly Sensitive Detection of Trace Cu(II) in Water

Sheng Chen,Rui Ding,Xiuling Ma,Liqun Xue,Xiuzhu Lin,Xiaoping Fan,Zhimin Luo

In this article, reduced graphene oxide (RGO)/carboxymethyl chitosan (CMC) composites (RGO/CMC) were synthesized by a hydrothermal method throughin-situreduction and modification of graphene oxide (GO) in the presence of CMC. An electrochemical sensor for the determination of Cu(II) by differential pulse anodic stripping voltammetry (DPASV) was constructed by an electrode modified with RGO/CMC. The fabricated electrochemical sensor shows a linear range of 0.02–1.2 μmol·L−1, a detection limit of 3.25 nmol·L−1(S/N = 3) and a sensitivity of 130.75 μA·μmol·L−1·cm−2, indicating the sensor has an excellent detection performance for Cu(II).Keywords:graphene;carboxymethyl chitosan;sensor;differential pulse anodic stripping voltammetry;Cu(II)

研究领域: 材料科学 · 环境科学 · 分析化学
✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2022 ·Vol. 169 ·期 3 ·037529 · IF 4.386

Blocking the Cu (II) Ions Mediated Catalytical Ability for Construction of Ratiometric Fluorescence Sensing Platform Based on Glutathione-Stabilized Copper Nanoclusters

Bei-Bei Tao,Ning-Ning Wu,Hong-Ding Zhang,Hai-Bo Wang

It is of great importance to integrate two kinds of fluorescent probes in one system to construct ratiometric sensing platform. Inspired by the efficient overlapped spectrum of glutathione-stabilized copper nanoclusters (GSH-CuNCs) and 2, 3-diaminophenazine (DAP), a novel and label-free ratiometric fluorescent sensor has been developed for Cu2+ and kojic acid (KA) detection on the basis of in situ converting o-phenylenediamine (OPD) into DAP by the catalytic oxidation ability of Cu2+. The Cu2+ catalytically generated DAP was served as an energy acceptor to inhibit the fluorescence emission of GSH-CuNCs (energy donor). As a result, the sensitivity and accuracy of the strategy were greatly improved due to the dual-emission reverse change ratiometric profile. The sensing system showed high sensitivity toward Cu2+ in a range of 0.1–50 μM and with a limit of detection of 20 nM. Furthermore, based on the specific coordination interaction between Cu2+ and KA, the ratiometric sensor displayed the range of detection of KA from 0.2 μM to 300 μM with a limit of detection of 50 nM. Thus, the ratiometric method paved a new way for the effective quantification of Cu2+ and KA in real samples, which were closely concerned with human health.

研究领域: 分析化学 · 生物医学
✓ 已验证 DOI 高影响因子
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