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MIL-100
LANGMUIR · 2023 · IF 3.9

MOF-Derived Hollow Spheres of MIL-100(Fe)-NH2(20) with Well-Developed Hierarchical Mesoporous and Uniform Distribution of Fe and N Active Phases for the Photocatalytic Removal of Organic Dyes

Suyun Wang,Yuanbo Fang,Wuli Han,Qiang Li,Xiao Luo

For the first time, MIL-100(Fe)-derived microspheres with a hollow structure were perfectly constructed and used as a photocatalyst to decompose organic dyes under visible light irradiation. The prepared MIL-100(Fe)-NH2(20) could boost the separation, migration, and transfer of photoinduced carriers effectively, together with efficient photocatalytic performance. In simulated sunlight, the MIL-100(Fe)-NH2(20) exhibits the best degradation efficiency as well as excellent reusability and stability, and the degradation rate for rhodamine B (RhB) can be more than 99.5% within 80 minutes. Structural analysis proves that the porous MIL-100(Fe)-NH2(20) catalyst reaps an amazing hollow structure, large specific surface areas (2784.9 m2·g–1), and uniform distribution of Fe and N active phases. Besides, the enhanced visible light response and lower recombination rate of e––h+ pairs are both confirmed, and the band gap is significantly reduced to 2.53 eV. Finally, the photocatalytic mechanism and the possible degradation pathway were suggested. Owing to the enhanced photocatalytic activity, good tolerance to pH and water quality, and excellent stability, the MIL-100(Fe)-NH2(20) catalyst can be potentially used in a wide range of dye wastewater purifications.

研究领域: 材料科学 · 环境科学
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Biomaterials Science · 2021 ·Vol. 9 ·期 20 ·6772-6786 · IF 6.843

Microneedle-mediated delivery of MIL-100(Fe) as a tumor microenvironment-responsive biodegradable nanoplatform for O2-evolving chemophototherapy

Sulan Luo,Yiting Zhao,Kewei Pan,Yixian Zhou,Guilan Quan,Xinguo Wen,Xin Pan,Chuanbin Wu

The low oxygen level in tumors significantly reduces the antitumor efficacy of photodynamic therapy (PDT). The provision of O2 and monomeric hydrophobic photosensitizers (PSs) under physiological conditions would greatly help to shrink malignant tumors. We take advantage of the high porosity and multifunctionality of metal–organic frameworks (MOFs) to fabricate a simple all-in-one nanoplatform mediated by microneedle delivery to achieve synergistic O2 evolution and chemophototherapy. An iron(III)-based MOF (MIL-100(Fe)) acted not only as a vehicle for the concurrent delivery of zinc phthalocyanine (ZnPc) and doxorubicin hydrochloride (Dox), but also to supply O2 by decomposing hydrogen peroxide (H2O2) in the tumor microenvironment via a Fenton-like reaction. In vitro and in vivo experiments indicated that the nanoplatform had excellent biocompatibility and exerted enhanced anticancer effects. The encapsulated drug was sustainably released from the nanoplatform skeleton in response to acidic tumor microenvironments. Moreover, upon 660 nm light irradiation, ZnPc effectively produced reactive oxygen species (ROS) due to the reduction of hypoxia by MIL-100(Fe). A microneedle technique was adopted to directly deliver the nanoplatform into superficial tumors rather than via systemic circulation. Hence, this study provides a new strategy for more efficient chemophototherapy of hypoxic superficial tumors.

研究领域: 癌症治疗 · 纳米技术 · 生物医学工程 · 药学
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JOURNAL OF FOOD SCIENCE · 2024 · IF 3.2

Development of a magnetic separation method for rapid isolation and enrichment of bacteria in raw pork using chitosan functionalized magnetic Fe3O4@MIL-100(Fe) composites

Juan Du,Zongshuang Li,Jiangli Guo,Kaidong Du,Zhijian Chen,Yanhong Bai

In this study, a pretreatment method based on a magnetic capture probe for the rapid isolation and enrichment of bacteria from raw pork was developed. The chitosan immobilized Fe 3 O 4 @MIL-100(Fe) was prepared as a capture probe for total bacterial counts through the electrostatic interaction of positively charged chitosan and the negatively charged substances on the surface of bacteria. The interference of matrix in pork samples on this method was studied and removed by differential centrifugation. The results showed the capture probe had a great selectivity binding and magnetic separation properties for the tested six common bacteria in pork. Under the optimal conditions, the capture efficiency of the bacteria (10 5 CFU mL −1 ) from pork surface samples was all above 90%. The capture efficiency of the bacteria in a homogenate system was greatly decreased due to the interference of sarcoplasmic protein and myofibrillar protein in pork. The matrix effect was mitigated by a differential centrifugation method, and the capture efficiency of all six bacteria was >80%. The developed magnetic separation method took 40 min and showed good isolation and enrichment properties of bacteria. Thus, the proposed method is expected to provide a simple, convenient, and time-saving pretreatment method for the detection of total bacterial counts in pork.

研究领域: 食品科学 · 微生物学 · 材料科学
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ANALYTICA CHIMICA ACTA · 2021 · IF 6.558

Facile in situ microwave synthesis of Fe3O4@MIL-100(Fe) exhibiting enhanced dual enzyme mimetic activities for colorimetric glutathione sensing

Jiabi Xu,Yanyan Xing,Yutong Liu,Mingzhe Liu,Xiaohong Hou

In recent decades, artificial nanozymes with excellent stability, low cost and availability have been gradually explored to avoid the limits of natural enzymes such as poor stability, high cost and difficult preparation. Herein, for the first time, we investigated the capability of nanoscale Fe 3 O 4 @MIL-100(Fe) as a nanozyme, which was quickly synthesized in situ by a microwave-assisted method within 20 min using Fe 3 O 4 as the metal precursor. The obtained Fe 3 O 4 @MIL-100(Fe) showed satisfactory intrinsic dual enzyme mimetic activities, including peroxidase (POD)- and catalase (CAT)-like activities. Moreover, a simple and effective colorimetric biosensor was fabricated to detect glutathione (GSH) based on its POD-like activity. The proposed measurement had a linear range of 1–45 μM and a limit of detection (LOD) of 0.26 μM (3.3 δ/S). It was proved that the established colorimetric sensing system could be successfully applied to detect GSH in actual biological samples. Importantly, the outstanding reusability and stability made it extremely valuable as a catalyst. The present work implied that Fe 3 O 4 @MIL-100(Fe) synthesized in situ by the microwave-assisted method was a very promising candidate for biocatalyst and biosensing.

研究领域: 纳米生物技术 · 分析化学 · 生物传感 · 酶模拟 · 分子诊断 · 转化医学
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ACS Omega · 2024 · IF 3.7

Oxaliplatin-Loaded Mil-100(Fe) for Chemotherapy–Ferroptosis Combined Therapy for Gastric Cancer

Boyao Sun,Xuewei Zheng,Xiaoyu Zhang,Huaiyu Zhang,Yang Jiang

Oxaliplatin (Oxa) is a commonly used chemotherapy drug in the treatment of gastric cancer, but its toxic side effects and drug resistance after long-term use have seriously limited its efficacy. Loading chemotherapy drugs with nanomaterials and delivering them to the tumor site are common ways to overcome the above problems. However, nanomaterials as carriers do not have therapeutic functions on their own, and the effect of single chemotherapy is relatively limited, so there is still room for progress in related research. Herein, we construct Oxa@Mil-100(Fe) nanocomposites by loading Oxa with a metal–organic framework (MOF) Mil-100(Fe) with high biocompatibility and a large specific surface area. The pore structure of Mil-100(Fe) is conducive to a large amount of Oxa loading with a drug-loading rate of up to 27.2%. Oxa@Mil-100(Fe) is responsive to the tumor microenvironment (TME) and can release Oxa and Fe3+ under external stimulation. On the one hand, Oxa can inhibit the synthesis of DNA and induce the apoptosis of gastric cancer cells. On the other hand, Fe3+ can clear overexpressed glutathione (GSH) in TME and be reduced to Fe2+, inhibiting the activity of glutathione peroxidase 4 (GPX4), leading to the accumulation of intracellular lipid peroxides (LPO), and at the same time releasing a large number of reactive oxygen species (ROS) through the Fenton reaction, inducing ferroptosis in gastric cancer cells. With the combination of apoptosis and ferroptosis, Oxa@Mil-100(Fe) shows a good therapeutic effect, and the killing effect on gastric cancer cells is obvious. In a nude mouse model of subcutaneous tumor transplantation, Oxa@Mil-100(Fe) shows a significant inhibitory effect on tumor growth, with an inhibition rate of nearly 60%. In addition to its excellent antitumor activity, Oxa@Mil-100(Fe) has no obvious toxic or side effects. This study provides a new idea and method for the combined treatment of gastric cancer.

研究领域: 癌症研究 · 纳米技术 · 药学 · 生物医学工程 · 分子生物学 · 治疗学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Probing the sites on metal oxide cluster nodes of metal organic framework MIL-96, MIL-100 and MIL-110

Yue Xiao,Haodong Huang,Shangpu Zhuang,Dong Yang

Metal oxide cluster MOF nodes are a good platform to understand the reactivities and catalysis. MIL-96, MIL-100 and MIL-110 are drastically different in their node structures. Following our previous reported results for MIL-100, we report the modified synthesis and characterization of the node sites of MIL-110 and MIL-96 and their catalytic sites by using methanol dehydration as probe reaction. We show that these MOFs can be synthesized from the same solution by adding various amounts of formic acid as modulator. Herein, the chemistry of hydroxyl, formate and methoxy groups were used to probe the three MOFs’ node sites. IR data show the bonding structures of these ligands are highly diverse, with reactivities and flexibilities depending on node sites. We identified terminal OH group and various µ 2 -OH groups in single, paired or hydrogen bonded modes on the MOF nodes. Formate ligands were introduced to the node sites during the synthesis or by a post treatment in formic acid/DMF solution. Surprisingly, the bonding modes of formate ligands on Al 3 (OH) 3 node structure of MIL-96 can be reversibly switched between monodentate and bidentate through a process induced by water molecules. Further, methoxy ligands—likely to be the intermediate for catalytic reaction—were also observed on the node sites under methanol dehydration conditions at 250 ℃. The activities of MIL-100 and MIL-96 for methanol dehydration determined by TOF per node were similar, both approximately 3-fold higher than that of MIL-110. The data suggests that catalytic sites incorporate adjacent vacancy and defect node sites, which constitute a minority among all observed MOF node sites. We foresee the opportunities in expanding the chemistry and understanding into other MOFs with metal oxide cluster nodes.

CAS / MDL: 920-42-3 64-18-6
研究领域: 材料科学 · 催化 · 化学工程 · 无机化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Efficient lithium extraction from aqueous solutions by MIL-100(Fe): A study on adsorption kinetics, thermodynamics and mechanism

Chengyu Huangfu,Shuning Yu,Bo Tong,Anni Yang,Jiafei Lyu,Xianghai Guo

MIL-100(Fe) is a kind of metal–organic frameworks (MOFs) with robust water and chemical stability. The adsorption kinetics, isotherms, thermodynamics and regeneration of MIL-100(Fe) were investigated to illustrate the process of efficient lithium adsorption. The adsorption kinetics of MIL-100(Fe) followed Pseudo-second-order model, and the lithium adsorption equilibrium was reached rapidly in 2 h. Langmuir model fit best with the adsorption isotherms, indicating chemisorption of lithium ions on MIL-100(Fe) and possibly a monolayer adsorption process. By calculating thermodynamic parameters (Δ G θ , Δ H θ and Δ S θ ), the adsorption of lithium on MIL-100(Fe) can be illustrated by a spontaneous endothermic process. The adsorption mechanism involved electrostatic interaction, impact of crystal defect sites and coordinative interactions between metal active sites and lithium ions (Fe—F‧‧‧Li). MIL-100(Fe) was regenerated for four cycles, and there was only a slightly decrease in adsorption capacity and the morphology remained stable. Combined with extremely short equilibrium time and high stability, MIL-100(Fe) can be a promising adsorbent for lithium extraction.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 化学工程 · 环境科学
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Journal of Environmental Chemical Engineering · 2020 · IF 4.3

Preparation of MIL-100(Fe) and multi-walled carbon nanotubes nanocomposite with high adsorption capacity towards Oxytetracycline from solution

Shanshan Chen,Zhongyang Zang,Shusheng Zhang,Gangfeng Ouyang,Runping Han

Metal-organic framework and nano carbon materials were widely used in separation field in recent years. In this study, nanocomposite of MIL-100(Fe) and multi-walled carbon nanotubes (MIL-100(Fe)-CNTs) was prepared and characterized and its adsorption property towards Oxytetracycline (OTC) was presented. MIL-100(Fe)-CNTs exhibits higher adsorption capacity compared to MIL-100(Fe), making this composite as one of the favorable adsorbents. The adsorption capacity of MIL-100(Fe)-CNTs reached 429 mg·g −1 at 313 K. The langmuir model and Koble-Corrigan model were better to predict the equilibrium data while the pseudo-second-order kinetic model could well describe the kinetic process. The process was endothermic and spontaneous while the ion exchange was the main adsorption mechanism of OTC on MIL-100(Fe)-CNTs. The nanocomposite is promising to effectively remove OTC from solution.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 环境科学 · 化学工程
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

A highly sensitive surface-enhanced Raman scattering sensor with MIL-100(Fe)/Au composites for detection of malachite green in fish pond water

Min Chen,Yiqun Huang,Junjian Miao,Yuxia Fan,Keqiang Lai

Concerns about food safety have been arisen due to the improper use of chemicals in aquaculture. Malachite green (MG) has attracted attention because of its illegal usage and its potential negative impacts on the environment and public health. Surface-enhanced Raman scattering (SERS) platforms coupled with different SERS substrates have been employed for rapid analysis of MG residues in food. However, the most commonly used SERS substrates were non-reusable and showed limited detection sensitivity. In this study, a novel SERS substrate with a good recyclability and a high sensitivity was prepared by electrostatically assembling together a metal–organic framework material called materials of institute lavoisie-100(Fe) (MIL-100(Fe)) and Au NPs. The lowest detectable concentration of MG was 10 −13 M based on the optimal substrate. The SERS sensor was applied for the detection of the trace MG in fish pond water, which was accomplished with the correlation coefficients R 2  = 0.991–0.996 in a concentration range of 10 −6 –10 −13 M. Moreover, MIL-100(Fe)/Au was recycled at least five times, realizing a “detection to degradation”, showing great potential for food contamination monitoring due to its distinguished performance.

CAS / MDL: 7782-61-8
研究领域: 分析化学 · 环境科学 · 食品安全
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DALTON TRANSACTIONS · 2025 · IF 3.3

Functionalized Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe) for Lithium Adsorption and Separation from Aqueous Solutions

Yanjia Zhou,Xiao-Dong Tang,Jingjing Li,Da-Yong Qing,Hong Wang

MIL-101(Cr) and MIL-100(Fe) are both representative MIL-type Metal-Organic-Frameworks (MOFs) materials, renowned for their large specific surface areas and size-tunable characteristics, making them suitable candidates for Li+ extraction from lithium-containing solvent. By introducing -NH2 functional groups and using LiNO3 as both a template and mineralizer, the functionalized MOF materials Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe) were synthesized. Following modification, their Li+ adsorption capacities were increased, reaching 43.58 and 38.22 mg/g, respectively. The dosage of mineralizer, initial Li+ concentration, adsorbent dosage, solution pH value, and temperature all have an impact on the adsorption capacity of adsorbents. In addition, through the establishment of the pseudo-first-order kinetic model, pseudo-second-order kinetic model, as well as Langmuir and Freundlich thermodynamic models, it can be known that the adsorption of the materials belonged to monolayer chemisorption, and the adsorption process was exothermic. Furthermore, both adsorbents showed good reusability, retaining over 85% of their initial adsorption capacity after four adsorption-desorption cycles, highlighting their practical applicability in lithium recovery processes. In Mg-Li mixed solution systems, both materials exhibited exceptional Li+ selectivity. At a low Mg2+/Li+ ratio of 3, the separation factor (α) exceeded 80; even at a high Mg2+/Li+ ratio of 10, α remained near 50. Additionally, in systems with coexistence of multiple interfering ions, the distribution coefficient (Kd) followed the order: Li+ ≫ Mg2+ > Ca2+ > Na+ > K+. In the mixed systems, Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe) exhibited certain separation effect for Li+ against competing cations.

研究领域: 材料科学 · 环境科学 · 化学工程 · 无机化学 · 分离技术
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JOURNAL OF NANOBIOTECHNOLOGY · 2022 ·Vol. 20 ·期 1 ·1-12 · IF 9.429

A UCMPs@MIL-100 based thermo-sensitive molecularly imprinted fluorescence sensor for effective detection of β-lactoglobulin allergen in milk products

Hong Liping,Pan Mingfei,Yang Xiao,Xie Xiaoqian,Liu Kaixin,Yang Jingying,Wang Shan,Wang Shuo

In this study, a thermo-sensitive molecularly imprinted fluorescence sensor was developed for the specific detection of β-Lactoglobulin (β-LG) allergen in milk products. The metal–organic frameworks (MIL-100) with a high specific surface area was coated on the surface of upconversion micro-particles (UCMPs). As the core, an imprinted polymer layer allowing for swelling and shrinking with response to temperature was prepared, which exhibited high adsorption and mass transfer capabilities for β-LG allergen. The fluorescence intensity of UCMPs@MIL-100@MIP decreased linearly with the concentration of β-LG in the range of 0.1–0.8 mg mL−1, and the limit of detection was 0.043 mg mL−1. The imprinting factor reached 3.415, which indicated that excellent specificity of the UCMPs@MIL-100@MIP for β-LG allergen. In the analysis of β-LG allergen in actual milk samples, the proposed UCMPs@MIL-100@MIP fluorescence sensor produced reliable and accurate results (recovery: 86.0–98.4%, RSD: 2.8–6.8%), closely related to the results of standard HPLC method (correlation coefficient: 0.9949), indicating that its feasibility in the detection of β-LG allergen.Graphical Abstract

研究领域: 分析化学 · 食品科学 · 材料科学 · 生物传感器
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Materials Today Communications · 2022 · IF 3.662

Activated metal-organic frameworks (a-MIL-100 (Fe)) as fillers in polymer electrolyte for high-performance all-solid-state lithium metal batteries

Tao Wei,Zhimeng Wang,Mi Zhang,Qi Zhang,Jiahao Lu,Yanyan Zhou,Cheng Sun,Zidong Yu,Yu Wang,Man Qiao,Sai Qin

As a common filler in polymer electrolytes , Metal-organic frameworks (MOFs) has been studied extensively in recent years. In this study, we propose a novel solid composite electrolytes (SCEs) based on PEO/LiTFSI/a-MIL-100 (Fe)/PVDF by using a straightforward solution-casting method. Unactivated and activated MIL-100 (Fe) (a-MIL-100 (Fe)) as the fillers were compared, and the interactions of functional groups of unactivated MIL-100 (Fe) and a-MIL-100 (Fe) with anions of electrolyte salts through Lewis acid-base interaction are studied with density functional theory (DFT) calculations. The influences of different a-MIL-100 (Fe) contents on electrochemical performances were also examined. The Li/SCEs/LiFePO 4 cell displayed high average discharge capacities of 161.8 mAh g −1 , 166.8 mAh g −1 , 158.9 mAh g −1 , 146.2 mAh g −1 and 92.6 mAh g −1 at the rate of 0.1, 0.2, 0.5, 1 and 2 C at 60 ℃, respectively, without liquid electrolytes. This work might provide new insight into the role of activated MOFs fillers in polymer electrolytes.

CAS / MDL: 90076-65-6 554-95-0
研究领域: 材料科学 · 电化学 · 能源存储
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