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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

An in-tube SPME–based analytical strategy for simultaneous determination of multi-residue pesticides in environmental water samples using a MWCNTs-COOH/Polypyrrole nanocomposite coating

Kemiao Nan,Ran Jia,Weibo Feng,Shize Qu,Qi Shen,Yan Lin,Bing Zheng,Xiaodong Ma

Currently, the application of SPME techniques for multi-residue pesticide analysis is highly limited. In this study, a polypyrrole (PPy) doped with carboxylated multi-walled carbon nanotubes (MWCNTs-COOH) in-tube solid-phase microextraction (IT-SPME) nanocomposite was designed and fabricated by the electrodeposition method. The preparation parameters, such as Py concentration and MWCNTs-COOH content, were optimized. The morphology and structure of the coating were evaluated using SEM and FT-IR which revealed a distributed coating with a coarse and fine grid-like structure, achieving the desired structural integration. Additionally, experimental factors affecting extraction efficiency were optimized, such as sample volume, eluent type, etc. This method indicated a great linear range of 1–500 μg L −1 and high correlation coefficients (R 2 ) above 0.9971. The limit of detection (S/N = 3) and quantification (S/ N  = 10) were 0.12–1.27 μg L −1 and 0.41–4.22 μg L −1 . The relative standard deviations (RSDs) for intra-day and inter-day analyses were in the ranges of 1.02–12.17% and 3.10–13.15%, respectively. The method achieved satisfactory spiked recovery rates ranging from 80.34% to 103.23%. Furthermore, MWCNTs-COOH/PPy coating holds outstanding stability and selectivity. Therefore, the developed IT-SPME approach was successfully used in the analysis of actual environmental water samples.

CAS / MDL: 109-97-7
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Polymers · 2025 ·Vol. 17 ·期 21 ·2879 · IF 4.9

UiO-66-(COOH)2 Decorated Collagen Fiber Membranes for High-Efficiency Separation of Cationic Surfactant-Stabilized Oil/Water Emulsions: Toward Sustainable and Robust Wastewater Treatment

Guifang Yang,Qiu Wu,Gao Xiao,Xiaoxia Ye

Membrane separation is a promising technology for emulsified wastewater treatment. However, conventional membrane often suffer from limitations such as low mechanical strength, the inherent “trade-off” effect between flux and separation efficiency, and poor antifouling properties. To address these challenges, we report a novel composite membrane (CFM-UiO-66-(COOH)2) fabricated by in situ growth of functionalized UiO-66-(COOH)2on a mechanically robust collagen fiber membrane (CFM) substrate. The resulting composite leverages the inherent properties of the CFM, along with the controlled generation of charge-neutralization demulsification sites and size-sieving filtration layers from the UiO-66-(COOH)2. This CFM-UiO-66-(COOH)2exhibited superwetting behavior and achieved efficient separation of cationic surfactant-stabilized oil-in-water micro- and nano-emulsions. Specifically, the CFM-UiO-66-(COOH)2achieved separation efficiencies exceeding 99.85% for various cationic O/W emulsions, with permeation fluxes ranging from 178.9 to 225.9 L·m−2·h−1. The membrane also demonstrated robust antifouling properties, excellent acid/alkali resistance, high abrasion durability, and good biocompatibility. Importantly, stable performance was maintained over six consecutive separation cycles. These characteristics, combined with the electrostatic interactions between carboxyl groups on the UiO-66-(COOH)2and cationic contaminants, suggest that CFM-UiO-66-(COOH)2holds significant potential for practical and sustainable wastewater treatment applications.

CAS / MDL: 140-72-7 57-09-0 89-05-4
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JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY · 2020 ·Vol. 20 ·期 4 ·2079-2086 · IF 1.134

Magnetic Fe3O4@SiO2@Ag@COOH NPs/Au Film with Hybrid Localized Surface Plasmon/Surface Plasmon Polariton Modes for Surface-Enhanced Raman Scattering Detection of Thiabendazole

Hu Xiangna,Bian XingZhong,Yu Shaozhou,Dan Kun

A magnetic Fe3O4@SiO2@Ag@COOH nanoparticle (NPs)/Au film was fabricated as an effective surface-enhanced Raman scattering (SERS) substrate through a combination of a solvothermal reaction, the Stöber method and an in-situ reaction. The superparamagnetic property of Fe3O4@SiO2@Ag and the decoration with –COOH groups allow efficient enrichment and capture of thiabendazole molecules. A large quantity of sub-10 nm gaps emerge when Ag NPs are decorated on the surface of the SiO2 shell, offering a dramatic electromagnetic field enhancement induced by localized surface plasmon resonance (LSPR). Finite-difference time-domain (FDTD) simulations show that strong near-field enhancement around the gap areas between the Ag NPs and Au film occurs, which is caused by the coupling between the LSPR of the Ag NPs and surface plasmon polaritons (SPPs) of the Au film. Due to the superparamagnetic property and high electromagnetic field enhancement, the Fe3O4@SiO2@Ag@COOH NPs/Au film as a SERS substrate can detect 1 μg/L thiabendazole in solution, showing great potential for SERS detection of environmental pollutants.

研究领域: 材料科学 · 环境科学
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BIOMACROMOLECULES · 2015 · IF 5.75

A Hierarchical Porous Bowl-like PLA@MSNs-COOH Composite for pH-Dominated Long-Term Controlled Release of Doxorubicin and Integrated Nanoparticle for Potential Second Treatment

Jianming Pan,Runrun Wu,Xiaohui Dai,Yijie Yin,Guoqing Pan,Minjia Meng,Weidong Shi,Yongsheng Yan

We chemically integrated mesoporous silica nanoparticles (MSNs) and macroporous bowl-like polylactic acid (pBPLA) matrix, for noninvasive electrostatic loading and long-term controlled doxorubicin (DOX) release, to prepare a hierarchical porous bowl-like pBPLA@MSNs-COOH composite with a nonspherical and hierarchical porous structure. Strong electrostatic interaction with DOX rendered excellent encapsulation efficiency (up to 90.14%) to the composite. DOX release showed pH-dominated drug release kinetics; thus, maintaining a weak acidic pH (e.g., 5.0) triggered sustained release, suggesting the composite’s great potential for long-term therapeutic approaches. In-vitro cell viability assays further confirmed that the composite was biocompatible and that the loaded drugs were pharmacologically active, exhibiting dosage-dependent cytotoxicity. Additionally, a wound-healing assay revealed the composite’s intrinsic ability to inhibit cell migration. Moreover, pH- and time-dependent leaching of the integrated MSNs due to pBPLA matrix degradation allow us to infer that the leached (and drug loaded) MSNs may be engulfed by cancer cells contributing to a second wave of DOX-mediated cytotoxicity following pH-triggered DOX release.

研究领域: 材料科学 · 药学 · 生物医学工程
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FOOD CHEMISTRY · 2021 · IF 7.514

A highly-sensitive and selective antibody-like sensor based on molecularly imprinted poly(L-arginine) on COOH-MWCNTs for electrochemical recognition and detection of deoxynivalenol

Weiqiang Li,Kaisheng Diao,Daoyang Qiu,Yifang Zeng,Kaijie Tang,Yifu Zhu,Yingying Sheng,Yangping Wen,Mingfang Li

A new strategy to mimic antibody for electrochemical recognition and detection of deoxynivalenol (DON) using a highly-sensitive and selective antibody-like sensor based on molecularly imprinted poly( l -arginine) (P-Arg-MIP) on carboxylic acid functionalized carbon nanotubes (COOH-MWCNTs) was proposed. l -arginine as functional monomer was screened to prepare imprinted electrode via its electro-polymerization in the presence of DON onto the surface of COOH-MWCNTs electrode coupled with theoretical calculation. Surface morphology, structural characteristics, and electrochemical properties of P-Arg-MIP/COOH-MWCNTs were characterized by SEM, EDS, FTIR, and CV, respectively. P-Arg-MIP/COOH-MWCNTs displayed relatively high conductivity, high effective surface area, antibody-like molecular recognition and affinity, and a good response towards DON in a linear range from 0.1 to 70 μM with LOD of 0.07 μM in wheat flour samples with satisfactory recovery and feasible practicability in comparison with HPLC. This method provides a promising biomimetic sensing platform for the determination of mycotoxins in food and agro-products.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Increasing electrochemical carbon dioxide reduction to methane via a novel copper-based conductive metal organic framework

Zhongyu Jing,Wenli Su,Yu Fan

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO 2 RR) to methane (CH 4 ) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO 2 RR to CH 4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO 2 RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH 4 reached 73.7 %, with a corresponding partial current density of −428.3 mA·cm −2 at −1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from −2.63 to −1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH 4 compared with those of the reference Cu-PD catalyst.

研究领域: 电化学 · 材料科学 · 催化 · 环境科学
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

A stable label-free electrochemical immunosensor based on AuNPs/Fe-MOFs/COOH-GO composites for the detection of non-small cell lung cancer marker CYFRA21-1

Fengjun Lv,Jinyi Chen,Shengxi Wu,Ran Sun,Lu Zhang,Yawen Luo,Hao Zhang,Doudou Xu

This study developed a stable, label-free AuNPs/Fe-MOFs/COOH-GO electrochemical immunosensor for the detection of Cytokeratin 19 fragment (CYFRA21-1), a critical biomarker for the early screening and diagnosis of non-small cell lung cancer (NSCLC). The nanocomposites of AuNPs/Fe-MOFs/COOH-GO was synthesized using a combination of hydrothermal synthesis, chemical reduction, and ultrasonic dispersion. AuNPs and COOH-GO components contributed high conductivity and a large specific surface area, which significantly enhanced the sensitivity of the sensor. The three-dimensional mesoporous structure of the Fe-MOFs further improved the stability of the immunosensor. Firstly, our novel nanocomposites was modified by using a glassy carbon electrode (GCE). CYFRA21-1 antibodies were then immobilized on the modified surface via interactions with thiol and carboxyl groups present on the nanomaterial. Bovine serum albumin (BSA) was employed to block non-specific binding sites. The constructed immunosensor exhibited a wide detection range for CYFRA21-1 from 1 pg mL −1 to 100,000 pg mL −1 , with a correlation coefficient (R 2 ) of 0.9989 in differential pulse voltammetry, and the limit of detection was defined as 0.35 pg mL −1 . The sensor also demonstrated high sensitivity, excellent specificity, good reproducibility, and remarkable stability, indicating its potent application potential for the early screening and diagnosis of NSCLC.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2025 · IF 21.1

CoOh-O-MnOh edge-sharing engineering in Co-Mn inverse spinel oxides for PMS activation: Electronic reconfiguration-driven nonradical oxidation via synergistic CoⅣ=O and 1O2

Qi Zhang,Wei Li,Siyuan Cao,Xu Yin,Hongwei Zhu,Liankai Gu,Haoming Chen,Xiaoyuan Zhang,Weiqing Han,Kajia Wei

Precisely controlling atomic occupancy in edge-sharing sites remains challenging and limits the application of spinel oxides in advanced oxidation processes (AOPs). Herein, a series of inverse spinel oxides featuring edge-sharing Co Oh -O-Mn Oh (Oh means octahedral) configurations were designed to leverage inter-octahedral electronic redistribution and spin-state modulation, thereby enhancing catalytic performance for peroxymonosulfate (PMS) activation and pollutant degradation. The energy redistribution induced by this structure enhances the O-p/Mn-d orbital hybridization, accelerates the electron transfer kinetics between Co and Mn, and promotes the generation of high-valent cobalt-oxo (Co IV =O) species and singlet oxygen ( 1 O 2 ), thereby increasing the degradation efficiency of organic pollutants. The optimized Co-Mn inverse spinel achieved complete BPA removal within 15 min, exhibiting 11.4-fold enhancement in PMS activation efficiency than unmodified cobalt oxide, and with < 6.5 % average efficiency deviation at 100 mM ionic concentration. This study offers a strategy for the precise design of edge-sharing reactive sites in inverse spinel oxides and their application in AOPs.

CAS / MDL: 70693-62-8 80-05-7
研究领域: 环境催化 · 高级氧化技术 · 材料化学 · 无机化学
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Construction of high conductivity poly(aryl ether ketone sulfone) proton exchange membrane by incorporating zwitterion-modified MOFs

Yuzhe Guo,Qingyuan Shi,Jiaxin Li,Youwei Huang,Jingmei Xu

In this paper, the zwitterion ADPS was modified on UiO-66-COOH by amidation reaction, and the functional UiO-66-ADPS that was produced was added to the matrix of sulfonated poly(aryl ether ketone sulfone) (SPAEKS), and the series of composite membranes of SPAEKS-UiO-66-ADPS (abbreviated as SPAEKS-U-A-X%) were successfully prepared. The UiO-66-ADPS and the series of composite membranes were characterized and evaluated. The composite membranes created exhibit excellent electrochemical performance, as well as superior water uptake and mechanical properties. Among them, at 90 °C, the proton conductivity of SPAEKS-U-A-0.75% reached 268.31 mS cm -1 , and the power density was 1553.10 mW/cm 2 , which was much higher than that of the SPAEKS membrane (302.65 mW/cm 2 ). The results show that UiO-66-ADPS significantly improved the electrochemical performance of the PEMs.

研究领域: 材料科学 · 高分子化学 · 能源材料 · 燃料电池 · 纳米复合材料
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CONSTRUCTION AND BUILDING MATERIALS · 2023 · IF 7.4

The reuse potential of spent ZIF-8@GO-COOH nano adsorption materials: Study on their impact on the hydration mechanism and mechanical properties of cement-based composites

Wei Yang,Ximing Zheng,Mingli Cao

Spent adsorbents often contain harmful substances, which may have an impact on the ecological environment if these substances enter the environment. This study mainly introduces a safe treatment method for solid waste formed after heavy metal ions are adsorbed by an efficient adsorbent, ZIF-8@GO-COOH. This work mainly discusses the impact of solidifying the spent adsorbent in the cement system on the cement mechanical properties and hydration process. The experimental results showed that when the dosage of the spent adsorbent was 0.01%, 0.02%, 0.03%, and 0.04%, respectively, the compressive strength of 28 d was increased by 4.24%, 6.16%, 7.19%, and 8.87%, respectively, compared with the cement without spent adsorbent. Introducing spent ZIF-8@GO-COOH in the cement production process does not have a negative impact on the cement mechanical properties, and can refine the cement pore structure and dense microstructure, thereby improving the compressive strength. The Toxicity Characteristic Leaching Procedure (TCLP) results showed that solidifying the spent adsorbent with cement can effectively reduce the leaching of heavy metal ions in the spent adsorbent. This study solidifies the spent ZIF-8@GO-COOH nanoadsorbent material into the cement system as a sustainable alternative to landfilling. This treatment method has certain economic benefits and safety, and has some reference significance for promoting the development and improvement of spent adsorbents and improving their safe treatment and reuse.

CAS / MDL: 64-17-5
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JOURNAL OF ALLOYS AND COMPOUNDS · 2025 · IF 6.3

Oxygen vacancy engineering in ZnO/PPy composites for enhanced electrocatalytic carbon dioxide reduction to synthesis gas

Cong Li,Nuramina Abdukirim,Tursun Abdiryim,Ruxangul Jamal,Feng Xu,Yaoming Yu,Sihuleng Ba

Oxygen vacancy (V O ) engineering is an effective strategy for enhancing the performance of electrocatalytic CO 2 reduction (eCO 2 RR) to CO. In this study, composite materials of zinc oxide (ZnO) and polypyrrole (PPy) were prepared via in situ polymerization, with the V O concentration precisely controlled by adjusting the PPy molar ratio. The V O concentration first increased and then decreased as the PPy content decreased, while the zinc vacancy (V Zn ) concentration exhibited an opposite trend. Characterization results indicate that the PPy conjugated framework dynamically regulates the V O /V Zn concentration through electron injection, and its controllable hydrophobicity enhances CO 2 mass transfer and interfacial enrichment. Crucially, experiments reveal that a high V O concentration is key to achieving high performance, as V O reduces the activation energy barrier for C O bond cleavage through charge redistribution, synergistically optimizing the adsorption energy of the *COOH intermediate. Density functional theory calculations confirm that Vo regulates the d-band center position of ZnO and reduces the activation energy barrier for CO 2 activation. The optimal sample, V O -enriched ZnO/PPy-4, achieves an FE CO of 73.8 % at −1.6 V (vs. RHE) and stably maintains CO/H 2 ratio of 2:1 at −1.2 V (vs. RHE), with < 5 % decay rover 8 h. This study demonstrates a strategy for obtaining high-performance electrocatalytic CO 2 reduction catalysts by regulating Vo concentration.

研究领域: 材料科学 · 电化学 · 催化 · 纳米技术 · 环境科学 · 化学工程
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 18 ·4193-4202 · IF 3.286

Fluorescent and mass spectrometric evaluation of the phagocytic internalization of a CD47-peptide modified drug-nanocarrier

Liu Chunlan,Yu Danxia,Ge Fuchun,Yang Limin,Wang Qiuquan

Ru(bpy) 3 @SiO 2 -COOH and Ru(bpy) 3 @SiO 2 @CD47-peptide nanoparticles (NPs) with fluorescent and mass spectrometric properties were designed and synthesized as the models of drug-nanocarriers. Their phagocytic internalization could be quantitatively measured using more sensitive inductively coupled plasma mass spectrometry (ICPMS) ( 102 Ru) versus traditional laser confocal scanning microscope ( λ ex/em  = 458/600 nm) for the first time. Modification of a self-signal trigging CD47-peptide on the NPs’ surface decreased internalization by 10 times, (2.79 ± 0.21) × 10 4 Ru(bpy) 3 @SiO 2 -COOH and (0.28 ± 0.04) × 10 4 Ru(bpy) 3 @SiO 2 @CD47-peptide NPs per RAW264.7 macrophage ( n  = 5). The alkynyl-linked CD47-peptide allowed us to quantify the number (2412 ± 250) of CD47-peptide modified on the NP and the total content (5.14 ± 0.25 amol) of signal regulatory protein α (SIRPα) on the macrophage by measuring the clickable tagged Eu using ICPMS. Furthermore, the interaction between CD47-peptide and SIRPα as well as the changes of the remaining free SIRPα during the internalization process of Ru(bpy) 3 @SiO 2 @CD47-peptide NPs were quantitatively evaluated, providing direct experimental evidence of the longspeculated crucial CD47-SIRPα interaction for drug-nanocarriers to escape internalization by phagocytic cells. Remarkable difference in the internalization ratio of 12.3 ± 4.8 of Ru(bpy) 3 @SiO 2 -COOH NPs and 4.3 ± 0.5 Ru(bpy) 3 @SiO 2 @CD47-peptide NPs with and without the protein corona indicated that CD47-peptide still worked when the protein corona formed. Not limited to the evaluation of the NPs studied here, such a fluorescent and mass spectrometric approach is very much expected to apply to the assessment of other drug-nanocarriers designed by chemists and before their medical applications. Graphical abstract

研究领域: 纳米技术 · 药理学 · 生物医学工程 · 分析化学
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