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MIL-101-NH2
International Journal of Nanomedicine · 2025 · IF 6.5

A Multifunctional MIL-101-NH2(Fe) Nanoplatform for Synergistic Melanoma Therapy

Jinlu Shang,Yongjun Chen,Fangliang Wang,Jing Yang,Yi Li,Liuxuan Yang,Xiuqiong Liu,Zhirong Zhong,Chaochi Yue,Meiling Zhou

Background Melanoma is an aggressive form of skin cancer, and single-modality treatments often fail to prevent tumor recurrence and metastasis. Combination therapy has emerged as an effective approach to improve treatment outcomes.Methods In this study, we developed a multifunctional nanoplatform, MIL@DOX@ICG, utilizing MIL-101-NH2(Fe) as a carrier to co-deliver the chemotherapeutic agent doxorubicin (DOX) and the photosensitizer indocyanine green (ICG). MIL-101-NH2(Fe) was synthesized via a hydrothermal method. Drug release was evaluated under different pH conditions, and the photothermal effect was tested under near-infrared (NIR) laser irradiation. Hydroxyl radical and reactive oxygen species generation capacities were quantified. Cellular studies using B16F10 cells assessed cytotoxicity, cellular uptake, migration inhibition, and colony formation suppression. In vivo experiments in melanoma-bearing mice evaluated antitumor efficacy and systemic safety through tumor growth inhibition, histological analyses, and toxicity assessments.Results MIL@DOX@ICG exhibited a uniform octahedral structure with a particle size of approximately 139 nm and high drug loading efficiencies for DOX (33.70%) and ICG (30.59%). The nanoplatform demonstrated pH-responsive drug release and potent photothermal effects. The generation of hydroxyl radicals via the Fenton reaction and reactive oxygen species production under NIR laser irradiation by MIL@DOX@ICG were confirmed. In vitro assessments revealed significant cytotoxicity of MIL@DOX@ICG against B16F10 cells under NIR laser irradiation, with improved efficacy in inhibiting cell proliferation and migration. In vivo studies confirmed the superior antitumor efficacy of MIL@DOX@ICG + NIR treatment, synergistically harnessing chemotherapy, photothermal therapy, photodynamic therapy, and chemodynamic therapy effects while maintaining excellent biocompatibility.Conclusion Our findings underscore the potential of MIL-101-NH2(Fe) nanoparticles as a versatile and effective platform for synergistic melanoma therapy, offering a promising strategy for overcoming the limitations of conventional treatment modalities.

CAS / MDL: 10312-55-7
研究领域: 肿瘤学 · 纳米医学 · 生物材料学
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RSC Advances · 2022 ·Vol. 12 ·期 38 ·24670-24680 · IF 4.036

Postsynthetic of MIL-101-NH2 MOFs supported on PVDF membrane for REEs recovery from waste phosphor

Wei Qin,Along Yu,Xue Han,Junwei Wang,Jiayin Sun,Jianli Zhang,Yaqing Weng

With the increasing demand for rare earth elements (REEs) due to their wide application in high technology, their recovery and separation from waste sources has gradually come onto the agenda. Herein, a new kind of MIL-101-NH2 (M1N) MOF functionalized with diethanol anhydride (DGA) incorporated into a polyvinylidene fluoride (PVDF) membrane (DGA-M1N@PVDF) has been fabricated for the sorption of REEs from a simulated acid leaching solution of waste phosphor, which contains a large amount of REEs. FTIR, TGA, XRD, fluorescence spectra and XPS analysis were used to characterize the synthesized composite membrane. Batch tests were employed to determine the optimal sorption conditions for Y and Eu adsorbed on DGA-M1N@PVDF adsorbent, such as pH (1–5), content of M1N MOFs (0–40 wt%), contact time (10–180 min) and ion concentration (0–20 mg L−1). Maximum adsorption capacities for Y and Eu on DGA-M1N@PVDF reached 991.7 μg g−1 and 98.76 μg g−1 for trace REE solution, respectively. Moreover, a pseudo-second-order kinetic model accurately described the sorption process, and the plotted isothermal data indicated that the Langmuir model was more suitable than the Freundlich model for Y and Eu sorption with monolayer and chemical adsorption. Meanwhile, FTIR and XPS analyses revealed that the Y and Eu adsorption on the DGA-M1N@PVDF composite membrane was mainly caused by the N and O atoms of the –CONH or –COOH groups coordinated with metal ions. Furthermore, after five cycles, the recovery efficiency by DGA-M1N@PVDF for REEs remains above 82% and the XRD patterns were consistent with the original sample, which implied that the DGA-M1N@PVDF membrane has preferable stability, recyclability and good efficiency in REE separation from waste phosphor solutions.

研究领域: 材料科学 · 环境工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2021 · IF 3.764

Integration of MIL-101-NH2 into Cellulosic Foams for Efficient Cr(VI) Reduction under Visible Light

Ju Liu,Dandan Hao,Huiwen Sun,Yu Li,Jianlin Han,Bo Fu,Jiancheng Zhou

In this Article, a hybrid foam was fabricated through the integration of amine-functionalized Fe-MOF (MIL-101-NH2) into cellulosic matrix. The existence of enormous group linkages and ionic bonding interactions among the composite foam network leads to a uniform dispersion of MIL-101-NH2 and high affinity between the MOF and cellulose skeleton. As-prepared hybrid foams were utilized as photocatalysts to reduce toxic hexavalent chromium ions (Cr(VI)) under visible light. Optimal performance was observed over CM-1 (with a MIL-101-NH2 and nanocellulose mass ratio of 1:1). When compared to pure MOF nanoparticle counterparts, the CM-1 foam presented preferable and more efficient Cr(VI) removal performance. The reasons could be attributed to the hierarchal pore structure and uniform MOF loading. Moreover, the flexible foams could be easily separated from the solution and preserved more than 80% removal efficiency of Cr(VI) after 10 runs. This work would shed light on how to construct high-efficiency photocatalysts for environmental governance from sustainable materials.

研究领域: 环境科学 · 材料科学
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2024 ·Vol. 31 ·期 6 ·9764-9783 · IF 0

Magnetically separable Co0.6Fe2.4O4/MIL-101-NH2 adsorbent for Congo red efficient removal

Zhang Zhenhong,Zhong Yuye,Sun Peng,Zhao Pingping,Li Houbin,Liu Xinghai

The development of effective and practical adsorbents for eliminating pollutants still remains a significant challenge. Herein, we synthesized a novel magnetically separable composite, Co 0.6 Fe 2.4 O 4 /MIL-101-NH 2 , through the in-situ growth of MIL-101-NH 2 on magnetic nanoparticles, designed specifically for the removal of Congo red (CR) from aqueous solutions. MIL-101-NH 2 possessed high BET surface area (240.485 m 2 •g −1 ) and facile magnetic separation function and can be swiftly separated (within 30 s) through an external magnetic field post-adsorption. The investigation systematically explored the influence of crucial parameters, including adsorbent dosage, pH, adsorption duration, temperature, and the presence of interfering ions, on CR adsorption performance. Findings indicate that CR adsorption adheres to the pseudo-second-order (PSO) kinetic model and the Langmuir isotherm model. Thermodynamic analysis reveals the spontaneity, endothermic nature, and orderly progression of the adsorption process. Remarkably, the adsorbent with 0.1 g•L −1 boasts an impressive maximum adsorption capacity of 1756.19 mg•g −1 for CR at 298.15 K, establishing its competitive advantage. The reuse of the adsorbent over 5 cycles remains 78% of the initial adsorption. The CR adsorption mechanisms were elucidated, emphasizing the roles of π-π interactions, electrostatic forces, hydrogen bonding, and metal coordination. Comparison with other dyes, such as methylene blue (MB) and methyl orange (MO), and exploration of adsorption performance in binary dye systems, demonstrates the superior capacity and selectivity of this adsorbent for CR. In conclusion, our magnetically separable metal–organic framework (MOF)based composite presents a versatile and effective solution for CR removal, with promising applications in water treatment and environmental remediation. Graphical

研究领域: 环境科学 · 材料科学 · 化学工程 · 纳米技术 · 物理化学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2024 · IF 20.2

Enhanced photocatalytic performance of 0.1Bi-MIL-101-NH2 after phosphorus adsorption: Synergistic effect of adsorption and photocatalysis

Yinghao Li,Ying Li,Qinglong Meng,Ke Jing,Jingyi Zhang,Qingyu Guan

Achieving efficient phosphorus recovery and reuse from wastewater presents formidable challenges. In this study, a synergistic adsorption photocatalysis process was successfully constructed. 0.1Bi-MIL-101-NH 2 showed the maximum phosphorus adsorption performance of 112 mg/g. After phosphorus adsorption, photoelectrochemical measurements confirmed that the photoelectric properties of the 0.1Bi-MIL-101-NH 2 -P sample was improved, and the degradation efficiency of SMX was increased by 20 % within 120 min. Meanwhile, the mineralization rate reached 91 %. The incorporation of Bi significantly enhanced the adsorption energy of the 0.1Bi-MIL-101-NH 2 sample. Notably, the presence of phosphorus on the surface of 0.1Bi-MIL-101-NH 2 -P enhanced the adsorption of water molecules by the material, thereby augmenting the generation of •OH. •O 2 - and •OH played dominant roles in the photodegradation of SMX. Finally, the degradation pathways of intermediates were further studied by Density functional theory (DFT) calculations and LC-MS analysis. This study provides a new avenue for phosphorus recovery and organic pollutant degradation.

CAS / MDL: 3317-61-1
研究领域: 环境科学 · 材料科学
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JOURNAL OF PHYSICAL CHEMISTRY B · 2024 · IF 2.8

Anchoring of Fe-MIL-101-NH2 to the Polymer Membrane Matrix through the Hinsberg Reaction to Promote Conductivity of SPEEK Membranes

Hong-Jie Zhang,Xue-Bin Shang,Xu-Ran Wang,Chen-Xi Zhang,Qing-Lun Wang

SCPEEK@MOF proton exchange membranes, where SCPEEK is sulfinyl chloride polyether ether ketone and MOF is a metal–organic framework, were prepared by doping Fe-MIL-101-NH2 into polymers. The amino group in the MOF and the -SOCl2 group in thionyl chloride polyether ether ketone cross-link to form a covalent bond through the Hinsberg reaction, and the prepared composite membrane has stronger stability than other electrostatic interactions and simple physical doping composite membranes. The formation of covalent bonds improves the water absorption of the composite membrane, which makes it easy for water molecules to form hydrogen bonds. Moreover, SPEEK as a proton conductive polymer and the synergy of MOFs improve the proton conductivity of composite membranes. The composite membranes were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The swelling rate, water absorption, mechanical stability, ion exchange capacity, and proton conductivity of the pure sulfonated polyether ether ketone (SPEEK) membrane were compared with those of the mechanically doped SPEEK/MOF membrane and the composite membrane SCPEEK@MOF doped with different ratios of Fe-MIL-101-NH2, and all of the SCPEEK@MOF showed superior performance. When the Fe-MIL-101-NH2 loading rate of the composite membrane is 2%, the proton conductivity of the composite membrane can reach 0.202 S cm–1 at 363 K and a 98% relative humidity, which is much higher than that of the SPEEK/MOF membrane obtained by simple physical doping under the same conditions.

研究领域: 材料科学 · 化学工程
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CATALYSIS TODAY · 2024 · IF 5.2

IL/MIL-101-NH2 heterogeneous catalyst prepared by acid-base self-assembly for hydrodeoxygenation of 2,5-tetrahydrofurandicarboxylic acid to adipic acid

Jiali Zheng,Zhihui Li,Dongsheng Zhang,Xinqiang Zhao,Qian Zhao,Yanji Wang

Bio-based route for preparing adipic acid (AA) from 5-hydroxymethylfurfural is the direction for achieving green and sustainable AA production. In light of the challenges, such as corrosion and difficulties in recycling of I - containing homogeneous catalyst, large amount, high cost, and significant mass transfer resistance of ionic liquid (IL) catalyst, encountered in the current hydrodeoxygenation of 2,5-tetrahydrofurandicarboxylic acid (THFDCA) to AA process. Herein, 1-sulfobutyl-3-methylimidazolium iodide IL ([HSO 3 -b-mim]·I) was used to functionalize MIL-101-NH 2 through acid-base self-assembly approach, hence, a heterogeneous catalyst, IL/MIL-101-NH 2 was designed and applied in the hydrodeoxygenation of THFDCA to bio-based AA for the first time. When reacted at 180 °C for 2 h, the THFDCA conversion and AA yield were 100 % and 99.9 %, respectively. Moreover, IL/MIL-101-NH 2 exhibited remarkable stability and could be reused multiple times with minimal loss in activity. XRD, SEM, FT-IR, BET, XPS, and TG results revealed that the functionalization process involved the reaction between HSO 3 in the IL and NH 2 in MIL-101-NH 2 , forming a salt that chemically bonded the IL to MIL-101-NH 2 , thereby enhancing stability. The excellent hydrodeoxygenation activity was attributed to the synergistic effect of the Lewis acid site (Cr 3+ ) and the Lewis base nucleophilic site (I - ) within IL/MIL-101-NH 2 .

研究领域: 化学工程 · 催化材料科学 · 绿色化学
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LANGMUIR · 2018 · IF 3.789

Metal–Organic Framework MIL-101-NH2-Supported Acetate-Based Butylimidazolium Ionic Liquid as a Highly Efficient Heterogeneous Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones

S. Y. Chong,T. T. Wang,L. C. Cheng,H. Y. Lv,M. Ji

A novel heterogeneous catalyst, the ionic liquid (IL) of 1-butyl-3-methylimidazolium acetate (BmimOAc) immobilized on MIL-101-NH2, denoted as IL(OAc–)-MIL-101-NH2, was prepared by the “ship-in-a-bottle” strategy. The IL of BmimOAc was prepared in the MIL-101-NH2 nanocages primordially, in which the condensation product of MIL-101-NH2’s amine group with 1,1′-carbonyldiimidazole (CDI) reacted with 1-bromo butane, and then the intermediate exchanged with potassium acetate. The structure and physicochemical properties of IL(OAc–)-MIL-101-NH2 were characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, DRS UV–vis, nitrogen adsorption–desorption, and elemental analysis. The results indicated that BmimOAc was anchored in the MIL-101-NH2 skeleton via the acylamino group and confined in the nanocages in the form of a single molecule. The composite material of IL(OAc–)-MIL-101-NH2 exhibited excellent catalytic activity and catalytically synthesized 3-aryl-2-oxazolone in an excellent yield of 92%. It can be reused up to six times without noteworthy loss of its activity and demonstrated distinct size-selective property for substrates. It was conjectured that the diffusion kinetics of reactants could be controlled by the aperture size of the metal–organic framework support.

研究领域: 材料化学 · 催化化学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2018 · IF 3.649

Acid-base bifunctional catalyst: Carboxyl ionic liquid immobilized on MIL-101-NH2 for rapid synthesis of propylene carbonate from CO2 and propylene oxide under facile solvent-free conditions

Tongtong Wang,Xuedan Song,Qunxing Luo,Xiaodong Yang,Siying Chong,Jie Zhang,Min Ji

In terms of ‘green chemistry’ and ‘atom economy’, the cycloaddition of CO 2 to yield cyclic carbonate without any additive is an eco-friendly way to utilize CO 2 . Unfortunately, the low CO 2 capture quantity of common catalysts limited its catalytic efficiency. Herein, a novel acid-base bifunctional catalyst was successfully prepared by immobilizing ionic liquid on MIL-101-NH 2 (IL/MIL-101-NH 2 ) and tested for propylene carbonate (PC) rapid and facile synthesis from CO 2 and propylene oxide (PO). The synergetic interaction between Lewis base with strong CO 2 chemical capture capacity and Brønsted acid with strong hydrogen bond donor leads to the high catalytic efficiency of IL/MIL-101-NH 2 for carbonate synthesis from CO 2 and PO without any additive. The immobilization mode between MIL-101-NH 2 and IL is energetically supported by the density functional theory (DFT) calculations. This design idea of specific catalyst and the acid-base synergetic strategy provides new insights into the design of powerful catalyst systems for the CO 2 conversion.

研究领域: 催化化学 · 环境科学 · 材料科学
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Penetrating the Blood–Brain Barrier for Targeted Treatment of Neurotoxicant Poisoning by Nanosustained-Released 2-PAM@VB1-MIL-101-NH2(Fe)

Dianfa Zhao,Jie Liu,Yunshan Zhou,Lijuan Zhang,Yuxu Zhong,Yang Yang,Baoquan Zhao,Mengru Yang,Yong’an Wang

It is very important to establish a sustained-release pralidoxime chloride (2-PAM) drug system with brain targeting function for the treatment of neurotoxicant poisoning. Herein, Vitamin B1 (VB1), also known as thiamine, which can specifically bind to the thiamine transporter on the surface of the blood–brain barrier, was incorporated onto the surface of MIL-101-NH2(Fe) nanoparticles with a size of ∼100 nm. Pralidoxime chloride was further loaded within the interior of the above resulted composite by soaking, and a resulting composite drug (denoted as 2-PAM@VB1-MIL-101-NH2(Fe)) with a loading capacity of 14.8% (wt) was obtained. The results showed that the drug release rate of the composite drug was increased in PBS solution with the increase of pH (2–7.4) and a maximum drug release rate of 77.5% at pH 4. Experiments on the treatment of poisoning by gavage with the nerve agent sarin in mice combined with atropine revealed that sustained release of 2-PAM from the composite drug was achieved for more than 72 h. Sustained and stable reactivation of poisoned acetylcholinesterase (AChE) was observed with an enzyme reactivation rate of 42.7% in the ocular blood samples at 72 h. By using both zebrafish brain and mouse brain as models, we found that the composite drug could effectively cross the blood–brain barrier and restore the AChE activity in the brain of poisoned mice. The composite drug is expected to be a stable therapeutic drug with brain targeting and prolonged drug release properties for nerve agent intoxication in the middle and late stages of treatment.

研究领域: 药学 · 纳米技术 · 神经科学 · 毒理学
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INTERNATIONAL JOURNAL OF ENERGY RESEARCH · 2022 ·Vol. 46 ·期 15 ·23480-23492 · IF 4.672

Enhancing proton conductivity of proton exchange membranes via anchoring imidazole-loaded MIL-101-NH2 onto sulfonated poly (arylene ether ketone sulfone) by chemical bonding

Lingxin Meng,Zhenguo Zhang,Mengchi Ju,Jingmei Xu,Zhe Wang

Summary Organic-inorganic modification by incorporating metal-organic frameworks to copolymers is one strategy to advance the properties of membranes. Here, the imidazole-loaded MIL-101-NH 2 (Im@MIL-101-NH 2 ) was prepared and chemically anchored onto sulfonated poly (arylene ether ketone sulfone) containing carboxyl groups (C-SPAEKS). The chemical stabilities, mechanical properties, and dimensional stabilities of compound membranes were increased. The highest tensile strength of C-SPAEKS-IM6 reach to 105.36 MPa. The weight retention rate of hybrid membranes was still higher than 90% after the oxidation stability test at 80°C. Furthermore, the introducing Im@MIL-101-NH 2 could construct new proton transport paths, and the amphiphilic imidazole molecules embedded inside Im@MIL-101-NH 2 could act as proton carriers. The C-SPAEKS-IM6 showed a maximum proton conductivity of 0.082 S cm −1 at 90°C. Additionally, the peak power density of C-SPAEKS-IM6 was 171.52 mW cm −2 . To sum up, this series of membranes have latent capacity in the application of fuel cells. Im@MIL-101-NH 2 was anchored on polymer backbones via the Hinsberg reaction. Chemical bonds between MOFs and polymer chains improved compatibility of two phases. Cross-linking structure enhanced the mechanical property and oxidative stability. The sulfonamide groups could devote protons and transport it to MOFs.

研究领域: 材料科学 · 化学 · 能源工程
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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Superior selective adsorption of anionic organic dyes by MIL-101 analogs: Regulation of adsorption driving forces by free amino groups in pore channels

Wei Zhang,Run-Zhi Zhang,Yun Yin,Ji-Min Yang

We herein report that the forces driving the adsorption of dyes onto MIL-101-NH 2 micro/nanoparticles, which are electrostatic , hydrogen bonding , and π-π stacking interactions, pore-volume, and steric hindrance , can be modulated by varying the molar ratio of terephthalic acid and 2-aminoterephthalic acid in the reaction system. The adsorption capacities of MIL-101-NH 2 -1 were determined to be 2967.1 mg g −1 for Congo red (CR), 461.7 mg g −1 for methyl orange (MO), and 259.8 mg g −1 for acid chrome blue K (AC), which were higher by 117.0%, 102.2%, and −19.6%, respectively, compared with those of pristine MIL-101. This adsorption behavior could be rationalized based on the molecular structure of the dye, its zeta potential , BET specific surface area, and the adsorption characteristics of the dye. The study revealed that free –NH 2 groups increase the hydrogen bonding and electrostatic interactions between MIL-101-NH 2 micro/nanoparticles and linear anionic dyes, thereby improving the adsorption performance for linear anionic dyes by overriding the effect of pore-volume. On the other hand, the increased steric hindrance between MIL-101-NH 2 micro/nanoparticles and a nonlinear anionic dye decreased the adsorption performance for the nonlinear dye, overriding the effects of hydrogen bonding, and electrostatic interactions. The adsorption uptakes of MIL-101-NH 2 -1 toward the linear anionic organic dyes (CR and MO) were found to be much higher than those of the other two MIL-101-NH 2 adsorbents investigated herein. However, the adsorption uptake of MIL-101-NH 2 -1 toward the nonlinear anionic organic dye (AC) was the smallest owing to different adsorption mechanisms. The adsorption performance of MIL-101-NH 2 is governed by the synergetic interplay between the hydrogen bonding, electrostatic and π–π stacking interactions, pore-volume, and the steric hindrance of the adsorbent.

CAS / MDL: 7789-02-8 75-59-2
研究领域: 材料科学 · 环境科学
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