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BIOTECHNOLOGY AND BIOPROCESS ENGINEERING · 2022 ·Vol. 27 ·期 1 ·135-144 · IF 3.386

Efficient Immobilization of Enzymes on Amino Functionalized MIL-125-NH2 Metal Organic Framework

Wang Zichen,Liu Yang,Li Jinhong,Meng Guoqing,Zhu Daoyu,Cui Jiandong,Jia Shiru

As a series of metal organic framework (MOFs), materials of institute lavoisier frameworks (MILs) are expected to be excellent supports for enzyme immobilization due to their good water-stability and acid tolerance. However, enzyme loading on MIL-125-NH 2 is very low due to small pore size and few amino groups on the surface of the MIL-125-NH 2 . In this work, catalase (CAT) was immobilized on the MIL-125-NH 2 and amino functionalized MIL-125-NH 2 by adsorption (CAT@MIL-125-NH 2 ) and covalent binding (CAT@Amino MIL-125-NH 2 ), respectively. Compared with the CAT@MIL-125-NH 2 and free CAT, the CAT@Amino MIL-125-NH 2 displayed high activity recovery, good pH stability, stability against denaturants, and thermostability. Furthermore, activity recovery of CAT@Amino MIL-125-NH 2 was 56% higher than CAT@MIL-125-NH 2 . The CAT@Amino MIL-125-NH 2 still retained 50% residual activity for 14 days at room temperature, whereas free CAT lost activity after storage for 1 day at the same storage conditions. Furthermore, the CAT@Amino MIL-125-NH 2 maintained 62% of its initial activity after 4 consecutive uses, showing good reusability. The results showed that the amino functionalized MIL-125-NH 2 is an excellent carrier of enzyme immobilization.

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Journal of Physical Chemistry C · 2021 · IF 4.126

Ag@MIL-101(Cr) Film Substrate with High SERS Enhancement Effect and Uniformity

Qinchao Shao,De Zhang,Cai-e Wang,Zhexiang Tang,Mingqiang Zou,Xiaobing Yang,Huaping Gong,Zhi Yu,Shangzhong Jin,Pei Liang

Surface-enhanced Raman scattering (SERS), owing to its high sensitivity and rapid response, has been widely used in various fields. However, it is still a challenge to prepare SERS substrates with high stability and reproducibility. Metal–organic frameworks (MOFs), with excellent enrichment capacity and stability, provide a new material for high-performance SERS substrates. In this paper, we prepare a MIL-101(Cr) film via a secondary growth method, and Ag+ is reduced to Ag NPs by UV irradiation and attach to the film to synthesize the Ag@MIL-101(Cr) film SERS substrate. Then, we change the time of UV light illumination and the amount of silver nitrate in order to obtain the optimal substrate. The detection capability of this sample can be up to 10–11 M for 4-ATP, and the relative standard deviation (RSD) is only about 5%, which demonstrates that the substrate has excellent SERS effect and reproducibility. Finally, the prepared substrate has been applied for the determination of nitrofurantoin, with its detection capability up to 10–7 M. This work proposes a simple method to synthesize MOF-based film substrate with high SERS performance and uniformity and provides potential for the sensitive detection of chemical or antibiotic residue.

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ANALYTICAL LETTERS · 2020 · IF 1.467

Fluorescent Determination of Mercury (II) and Glutathione Using Amino-MIL-53(Al) Nanosheets

Meijuan Ren,Huan Wang,Yuanyuan Liu,Qin Ma,Wenjing Jia,Mingzhu Liu,Huiju Wang,Yongchang Lu

Amino-MIL-53(Al) nanosheets were synthesized by a hydrothermal reaction and were employed as a fluorescent probe because of their high quantum yield and excellent stability. The amino-MIL-53(Al) nanosheets have a maximum fluorescence emission peak at 435 nm using an excitation wavelength of 335 nm. The fluorescent intensity of luminophor at 435 nm was linearly quenched when mercury (II) (Hg2+) was added, which occurred due to the adsorption of Hg2+ onto the luminophor surface. Under these conditions, the fluorescent signal of the system is in the “turn-off” state. Following the addition of glutathione (GSH) into the system, the quenched fluorescence intensity may be partially restored based on the reaction between glutathione and Hg2+. In this condition, the fluorescent signal of the amino-MIL-53(Al)-Hg2+ system is in the “turn-on” state. Therefore, the amino-MIL-53(Al) nanosheets were successfully used as a “turn-off-on” fluorescent sensing system to determine the concentrations of Hg2+ in Tibetan medicine and glutathione in rabbit serum. A good correlation coefficient was obtained between the quenching of the fluorescence intensity of luminophor and the concentration of Hg2+ using the optimized conditions. A linear range was acquired from 1.96 nM to 38.27 μM with a detection limit of 0.23 nM of Hg2+ based upon a signal-to-noise ratio of three. For glutathione, the linear dynamic range was from 210 nM to 15.25 μM with a detection limit equal to 8.11 nM based upon a signal-to-noise ratio of three. This developed sensor system has the advantages of high selectivity, favorable sensitivity and simple operation for the determination of Hg2+ and glutathione in real samples.

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RSC Advances · 2021 ·Vol. 11 ·期 4 ·2397-2404 · IF 3.361

Ratio fluorescence detection of tetracycline by a Eu3+/NH2-MIL-53(Al) composite

Jing Chen,Yali Xu,Shuying Li,Fanghong Xu,Qian Zhang

Tetracycline detection has been a great concern because of its overuse and difficulty in degrading. Here, a detection method with ratio fluorescence was developed by synthesizing Eu3+ doped nanocomposites with NH2-MIL-53(Al) nanosheets. After adding tetracycline, the fluorescence intensity at 616 nm characteristic emission peak of Eu3+ was sensitized by the antenna effect generated from coordinating Eu3+ with tetracycline, but the fluorescence of NH2-MIL-53(Al) at 433 nm was quenched by the fluorescence resonance energy transfer between the Eu3+-tetracycline composition and NH2-MIL-53(Al). Therefore, the efficient detection of tetracycline was achieved based on this change of ratio fluorescence signal. The experimental results show that Eu3+/NH2-MIL-53(Al) has excellent selectivity, a wider linear range and a lower detection limit for detecting tetracycline. This method can afford favorable ideas for developing advanced chemical and biological sensors.

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Journal of Chemistry · 2020 · IF 1.79

Hydrothermal Catalytic Conversion of Glucose into Lactic Acid with Acidic MIL-101(Fe)

Xiaofang Liu,Zhigang Liu,Qiuyun Zhang,Hongguo Wu,Rui Wang

MIL-101(Fe) was explored for the first time for the catalytic conversion of glucose into lactic acid (LA). The as-synthesized MIL-101(Fe) was successfully characterized, and its higher specific surface area, porosity, and feasible acid properties were confirmed to determine the remarkable catalytic activity in glucose-to-LA conversion (up to 25.4% yield) compared with other catalysts like MIL-101(Cr, Al) and UiO-66(Zr). The reaction parameters including temperature, reaction time, and substrate species as well as catalyst reusability were discussed.

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Journal of Analysis and Testing · 2019 ·Vol. 3 ·期 3 ·238-245 · IF 0

CNT-Modified MIL-88(NH2)-Fe for Enhancing DNA-Regulated Peroxidase-Like Activity

Sun Shihao,Fan Yaofang,Du Jiaoyang,Song Zhilian,Zhao Huimin

Over the past few decades, the enzyme-mimicking activity of metal–organic frameworks (MOFs) accompanied with structural characteristics has aroused much attention. However, pure MOFs have low affinity with DNA. Here, iron-based MOFs with acidized carbon nanotubes (CNTs) via a simple hydrothermal process have been synthesized, named as MIL-88(NH 2 )-Fe@CNTs. CNTs can enhance the affinity between MOF and DNA, achieving flexible regulation of their catalytic activity benefiting from the strong π − π stacking between CNTs and DNA. Meanwhile, in comparison with conventional iron-based MOFs, the addition of CNTs, which contributes to the acceleration of electron transfer, endowing as-prepared nanocomposites remarkably enhanced peroxidase-like activity to achieve an ultrasensitive detection of H 2 O 2 with the LOD of 17.64 μg/L. Notably, the as-prepared nanocomposites with adsorbed DNA displayed excellent affinity towards both TMB (3, 3′, 5, 5′-tetramethylbenzidine) substrates and H 2 O 2 as well as high catalytic velocity. On the basis of their switchable peroxidase-like activity regulated by different length or sequence of ssDNA, it is believed that our-prepared MOF-based nanomaterials would be promising for fabricating versatile and sensitive label-free colorimetric assays for diverse targets.

CAS / MDL: 54827-17-7
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JOURNAL OF POROUS MATERIALS · 2019 ·Vol. 26 ·期 6 ·1839-1850 · IF 1.947

Degradation of tetracycline by a novel MIL-101(Fe)/TiO2 composite with persulfate

He Lei,Zhang Yaqin,Zheng Yane,Jia Qingming,Shan Shaoyun,Dong Yanan

An effective catalyst of MIL-101(Fe)/TiO 2 composite was synthesized by solvothermal method. The resultant MIL-101(Fe)/TiO 2 was used for advanced oxidation degradation of tetracycline (TC) for the first time. The results indicated that the MIL-101(Fe)/TiO 2 showed higher TC degradation efficiency than pure MIL-101(Fe) or TiO 2 with the persulfate. Using 1 g L −1 MIL-101(Fe)/TiO 2 and persulfate at pH 7, 90.15% degradation rate was achieved under xenon lamp irradiation in 5 min for 20 mg L −1 TC. TiO 2 introduced in the composite played an important role in the degradation process, in which TiO 2 had a synergetic effect with Fe 3+ to generate Fe 2+ , Ti 3+ and radicals. Fe 2+ reacted with persulfate to produce Fe 3+ and a number of · OH to degrade TC. This reaction process was so fast that MIL-101(Fe)/TiO 2 with persulfate could degrade TC fairly rapidly. A novel TiO 2 -based metal–organic frameworks (MOFs) composite was more efficient for degrading pharmaceutical wastewater.

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JOURNAL OF SOLID STATE CHEMISTRY · 2024 · IF 3.2

Coupled DMF and H2O photocatalytic hydrogen production via ZnIn2S4@MIL-125(Ti) heterojunction

Ziqiang Zhang,Zhengfeng Shen,Chuanyu Zhu,Yunfang Wang,Yawen Wang,Caimei Fan,Rui Li,Jianxin Liu

Producing hydrogen from organic/inorganic hydrides is an innovative clean energy alternative to fossil fuels , addressing the increasing energy demands. Here, we first propose coupled photocatalytic water hydrogen production and N,N-dimethylformamide (DMF, C 3 H 7 NO) dehydrogenation technology to obtain high value-added H 2 and N,N-dimethylcarbamic acid (C 3 H 7 NO 2 ). ZnIn 2 S 4 @MIL-125(Ti) nanoheterostructures were synthesized using a simple solvothermal method and resulting in a photocatalytic H 2 production rate of 2.135 mmol h −1  g −1 (apparent quantum efficiency at 380 nm was 2.6 %) which is 2.77 times higher than pure ZnIn 2 S 4 . Liquid-phase mass spectrometry indicates that the DMF oxidation activity of ZIS@MIL heterojunction is double pure ZnIn 2 S 4 and only microcrystalline CO 2 is produced. Isotopes indicate that the production pathway of H 2 results from the coupling of the –CHO bond in DMF and the –H in water. The improved photocatalytic activity of the ZnIn 2 S 4 @MIL-125(Ti) heterostructure is attributed to facilitating efficient charge carrier transfer and separation and DMF depletion of holes accelerates electron transfer .

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JOURNAL OF POROUS MATERIALS · 2025 · IF 3.2

Degradation of tetracycline by MIL-101(Fe)/CoFe2O4 activated persulfate under visible light

Rui Guofen,Hu Zihao,Wu Huiqi,Ma Jianfeng

Composites of MIL-101(Fe)/CoFe 2 O 4 were prepared by a simple solvothermal approach and these composites were explored for tetracycline (TC) degradation by using light and persulfate (PS). MIL-101(Fe)/CoFe 2 O 4 catalyst showed superior catalytic performance when combined with photocatalysis and chemical catalysis. Experimental results suggest that the degradation efficiency reached 83% within 40 min. The TC adsorption ability of MIL-101(Fe)/CoFe 2 O 4 was tightly associated with pH, which can be interpreted through isoelectric point. Oxygen-active species, containing singlet oxygen ( 1 O 2 ) or superoxide radicals (O· 2‾), were also generated when there was dissolved oxygen, which could decompose the TC organic contaminant in solution. To be specific, MIL-101(Fe)/CoFe 2 O 4 /PS/Vis catalytic system was capable of eliminating TC through forming h + , 1 O 2 , O· 2‾, hydroxyl radicals (·OH) and sulfate radicals (·SO 4 ‾) species. Moreover, MIL-101(Fe)/CoFe 2 O 4 composite material showed outstanding stability.

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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Highly permeable MOF NH2-MIL-101(Cr) fragment membranes for CO2/N2 separation

Yunqi Zhou,Ye Yuan,Xinlei Liu,Zhi Wang

Metal-organic framework (MOF) membranes with proper pore size distribution and functional groups are generally more suitable for separation. Most MOFs are characterized by a hierarchical pore structure, which possesses large cavities surrounded by small windows. Fabrication of MOF membranes only retaining microporous fragment structure is a workable method to narrow pore size distribution. In this study, well-grown NH 2 -MIL-101(Cr) fragment membranes were fabricated for CO 2 separation by adjusting acetic acid – ligand – metal ratio to balance the nucleation and growth. NH 2 -MIL-101(Cr) fragment has a similar chemical structure to NH 2 -MIL-101(Cr) as expected, but only small pores with size around 0.56 nm is retained. The NH 2 -MIL-101(Cr) fragment membranes exhibited CO 2 /N 2 selectivity of about 37 with CO 2 permeance up to 6104 GPU.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Fe2+-Triggered Unexpected Room Temperature H2S Catalytic Oxidation Activity in MIL-100(Fe)

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

The abundant Fe 3+ Lewis acidic sites and well-developed pore structure endow the Fe-MOFs with great potential for H 2 S catalytic oxidation at room temperature, but their performance is inferior owing to the insufficient redox ability of the Fe 3+ species inherent in frameworks. Herein, an effective protocol was proposed for the first time to remarkably improve the catalytic oxidation performance of MIL-100(Fe) under ambient conditions through the introduction of Fe 2+ coordinatively unsaturated site (CUS) species into the framework. As expected, the sample after modification had a superior H 2 S breakthrough capacity of 267.3 mg S/g, an 18.4-fold increase compared with that without Fe 2+ CUS (14.5 mg S/g). The introduced Fe 2+ species triggered the Fe 3+ /Fe 2+ redox cycle for H 2 S catalytic oxidation by enhancing the oxidative ability of the Fe 3+ CUS intrinsic to the framework. Moreover, the Fe 2+ CUS was also found act as an active site for O 2 activation into O 2 ∙– , which not only provides an additional pathway for H 2 S catalytic oxidation but also accelerates the redox cycling of Fe 3+ /Fe 2+ during the catalytic oxidation process. On the basis of the experimental findings, a plausible catalytic mechanism involving mixed-valence iron sites in MIL-100(Fe) was proposed.

CAS / MDL: 7664-39-3 554-95-0
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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.

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