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Nanomaterials · 2018 ·Vol. 8 ·期 6 ·446 · IF 3.504

MIL-100(Al) Gels as an Excellent Platform Loaded with Doxorubicin Hydrochloride for pH-Triggered Drug Release and Anticancer Effect

Yuge Feng,Chengliang Wang,Fei Ke,Jianye Zang,Junfa Zhu

Slow and controlled release systems for drugs have attracted increasing interest recently. A highly efficient metal-organic gel (MOGs) drug delivery carrier, i.e., MIL-100(Al) gel, has been fabricated by a facile, low cost, and environmentally friendly one-pot process. The unique structure of MIL-100(Al) gels has led to a high loading efficiency (620 mg/g) towards doxorubicin hydrochloride (DOX) as a kind of anticancer drug. DOX-loaded MOGs exhibited high stability under physiological conditions and sustained release capacity of DOX for up to three days (under acidic environments). They further showed sustained drug release behavior and excellent antitumor effects in in vitro experiments on HeLa cells, in contrast with the extremely low biotoxicity of MOGs. Our work provides a promising way for anticancer therapy by utilizing this MOGs-based drug delivery system as an efficient and safe vehicle.Keywords:metal-organic gels;doxorubicin loading and release;pH-responsiveness;anticancer effect

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JOURNAL OF CATALYSIS · 2018 · IF 6.759

Dynamic kinetic resolution of amines by using palladium nanoparticles confined inside the cages of amine-modified MIL-101 and lipase

Sen Xu,Meng Wang,Bo Feng,Xinchen Han,Zijie Lan,Huajun Gu,Hexing Li,Hui Li

Dynamic kinetic resolution (DKR) of amines is an important strategy for the synthesis of chiral drugs and their building blocks; however, improving the matchability of metal-catalyzed racemization and enzymatic resolution is still a task. In this paper, Pd nanoparticles (NPs) were encapsulated inside the cages of ethylenediamine-grafted MIL-101 (ED-MIL-101), giving highly efficient catalysts (Pd/ED-MIL-101) for the racemization of primary amines. The racemization can be combined with lipase-catalyzed resolution in a one-pot DKR of rac -1-phenylethylamine leading to optically pure product (>99% ee value) with an excellent conversion and selectivity up to 99% and 93%, respectively, superior to other catalysts, such as Pd/MIL-101, Pd/MCM-41 and commercially available Pd/C. Furthermore, the heterogeneous chemoenzymatic catalyst combination can be recovered and recycled 8 times without significant loss of efficiency. The enhance catalytic performances were found to depend on the amine modification of MIL-101 that not only endows the surface of its cages with basic property, but also enables efficiently confining Pd NPs in the cages. In addition, the matchability of such chemoenzymatic catalyst combination can be further enhanced by conducting the DKR process under microwave irradiation.

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2018 ·Vol. 29 ·期 23 ·20356-20366 · IF 2.324

Synthesis and enhanced visible light-induced photocatalytic activity of a hierarchical porous biomorphic N/Zn–TiO2@NH2-MIL-125 photocatalyst

Du Yingying,Zhao Lei,Chen Hui,Huang Zhaohui,He Xuan,Fang Wei,Li Weixin,Zhang Fuqing,Wang Guanghui

Heterojunction is considered as very promising material for various applications in photocatalysis. Herein, an efficient heterojunction photocatalyst N/Zn–TiO 2 @NH 2 -MIL-125 was successfully synthesized for photo-degradation organic oxidation by biological-templated method. The electron–hole pairs can be separated in space more efficiently because of heterojunction structure. Systematical analyses of spectroscopy and microscopy measurements revealed that N/Zn–TiO 2 @NH 2 -MIL-125 heterojunction materials exhibited hierarchical porous structure with high surface area of 366.02 m 2  g −1 and outstanding optical properties. Photocatalytic activity was investigated by degradating of rhodamine B (1000 µM) under visible-light irradiation. The N/Zn–TiO 2 @NH 2 -MIL-125 showed enhanced photocatalytic activity for RhB degradation, which is respectively about 1.81 and 1.97 times higher than that of the pristine N/Zn–TiO 2 and NH 2 -MIL-125. Various advanced spectroscopic characterizations were applied including photoluminescence, Mott–Schottky curves and electrochemical impedance spectroscopy. A possible mechanism of enhanced photocatalytic oxidation activity for N/Zn–TiO 2 @NH 2 -MIL-125 composite under visible light irradiation was discussed.

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Analytical Methods · 2014 ·Vol. 7 ·期 4 ·1463-1470 · IF 1.938

Investigation of the adsorption behaviour of different types of dyes on MIL-100(Fe) and their removal from natural water

Yaoyao Jia,Qing Jin,Yan Li,Yuxiu Sun,Jianzhong Huo,Xiaojun Zhao

Metal–organic framework MIL-100(Fe) has high surface area, mesoporous cages, metal active sites and excellent water stability. These fascinating properties endow MIL-100(Fe) with the potential to extract organic dyes from environmental water samples. In the present work, MIL-100(Fe) is synthesized and applied as an adsorbent to remove three different types of dyes from aqueous solution in view of assessing the adsorption isotherms, kinetics and thermodynamics, desorption, and adsorbent regeneration. The adsorption for methylene blue and methyl blue follows a pseudo-second-order kinetics and fits the Freundlich model. The adsorption is a spontaneous process, but is controlled by different thermodynamic parameter changes. Moreover, MIL-100(Fe) could hardly adsorb isatin. Variables influencing the adsorption efficiency, such as adsorption time, temperature, solution pH, adsorbent dosage and salt concentration, are investigated. No remarkable effects of pH and ionic strength are observed for the adsorption of methylene blue and methyl blue on MIL-100(Fe). The used MIL-100(Fe) could be regenerated effectively and recycled without a significant loss of adsorption ability. The adsorption efficiency is about 100% for methylene blue and 52.1% for methyl blue, and the developed method is applied to remove two types of dyes in local water samples.

CAS / MDL: 554-95-0
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Nano Life · 2015 · IF 0

MIL-101/GO Coated Stir Bar for SBSE to Determine Azo Dyes in Water Samples by UV–Vis Spectrophotometric Method

Qiong Yi,Ling Li,Wei Hong,Lu Fan

A composite of chromium (III) terephthalate metal-organic framework and graphene oxide (MIL-101/GO) coated stir bar was prepared by sol–gel technique for the first time and was employed for stir bar sorptive extraction (SBSE) of trace azo dyes amaranth, sunset yellow and carmine from water samples followed by UV–Vis spectrophotometric detection. A MIL-101/GO coating was first created on the glass bar surface. MIL-101/GO and MIL-101/GO coated stir bars were characterized. The enrichment factors of azo dyes by SBSE have been investigated in detail, and the optimized experimental parameters were obtained. Under the optimal conditions, a method for determination of trace amount of azo dyes was setup, and the detection limits of amaranth, sunset yellow and carmine were 2.3 ng/mL, 1.7 ng/mL and 1.6 ng/mL. The proposed method was successfully applied for the analysis of the three azo dyes in water samples.

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JOURNAL OF HAZARDOUS MATERIALS · 2015 · IF 4.529

MIL-53(Fe) as a highly efficient bifunctional photocatalyst for the simultaneous reduction of Cr(VI) and oxidation of dyes

Ruowen Liang,Fenfen Jing,Lijuan Shen,Na Qin,Ling Wu

A bifunctional photocatalyst-Fe-benzenedicarboxylate (MIL-53(Fe)) has been synthesized successfully via a facile solvothermal method. The resulting MIL-53(Fe) photocatalyst exhibited an excellent visible light ( λ   ≥   420   nm) photocatalytic activity for the reduction of Cr(VI), the reduction rate have reached about 100% after 40   min of visible light irradiation, which has been more efficient than that of N-doped TiO 2 (85%) under identical experimental conditions. Further experimental results have revealed that the photocatalytic activity of MIL-53(Fe) for the reduction of Cr(VI) can be drastically affected by the pH value of the reaction solution, the hole scavenger and atmosphere. Moreover, MIL-53(Fe) has exhibited considerable photocatalytic activity in the mixed systems (Cr(VI)/dyes). After 6   h of visible light illumination, the reduction ratio of Cr(VI) and the degradation ratio of dyes have been exceed 60% and 80%, respectively. More significantly, the synergistic effect can also be found during the process of photocatalytic treatment of Cr(VI) contained wastewater under the same photocatalytic reaction conditions, which makes it a potential candidate for environmental restoration. Finally, a possible reaction mechanism has also been investigated in detail.

CAS / MDL: 10025-77-1
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CHEMICAL PAPERS · 2017 ·Vol. 72 ·期 1 ·235-250 · IF 1.258

A novel catalyst of MIL-101(Fe) doped with Co and Cu as persulfate activator: synthesis, characterization, and catalytic performance

Duan Mei-Juan,Guan Ze-yu,Ma Yong-Wen,Wan Jin-Quan,Wang Yan,Qu Yan-Fei

In this work, effective and novel heterogeneous catalysts of Metal–organic framework MIL-101(Fe) doped with cobalt (Co 2+ ) or copper (Cu 2+ ) have been synthesized by post-synthesis method, namely Co–MIL-101(Fe) and Cu–MIL-101(Fe). The initial and metal-doped samples were tested to activate persulfate (PS) for removal of Acid Orange 7 (AO7) in water. The surface of samples were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, N 2 adsorption, scanning electron microscopy and transmission electron microscopy. The addition of Cu 2+ and Co 2+ could alter structure characteristics of MIL-101(Fe) in crystal structure and morphology. The unusual octahedron morphology of MIL-101(Fe) turned to be irregular, disorder and a rod-like morphology was shaped. What is more, Co doping caused greater changes in structure characteristics in comparison with Cu doping. The alteration was reflected in the catalytic capacity of PS activation. An interesting note was that, whether Co or Cu doping, metal-doped MIL-101(Fe) greatly improved the PS activation as compared to unmodified MIL-101(Fe). The removal rate of AO7 was about 66, 92, 98% in MIL-101(Fe)/PS, 6%wtCu–MIL-101(Fe)/PS and 6%wtCo–MIL-101(Fe)/PS system, respectively. Some results also suggested the performance of Co–MIL-101(Fe) was superior to that of Cu–MIL-101(Fe). Additionally, a series of parameters were designed to achieve maximum capacity of PS activation. Such an enhancement in activity may be attributed to the main reasons: the new active sites created by metal additives; an increase in number of active Fe sites produced by Co and Cu doping which results in alteration of morphology and structure of catalysts.

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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2016 ·Vol. 23 ·期 15 ·15218-15226 · IF 2.76

Core-shell Fe3O4@MIL-101(Fe) composites as heterogeneous catalysts of persulfate activation for the removal of Acid Orange 7

Yue Xinxin,Guo Weilin,Li Xianghui,Zhou Haihong,Wang Ruiqin

In this study, a novel core-shell Fe 3 O 4 @MIL-101 (MIL stands for Materials of Institute Lavoisier) composite was successfully synthesized by hydrothermal method and was fully characterized by X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectra, and X-ray photoelectron spectroscopy. The composite was introduced as a catalyst to generate powerful radicals from persulfate for the removal of Acid Orange 7 in an aqueous solution. Effects of the central metal ions of MIL-101, amino group content of MIL-101, and pH were evaluated in batch experiments. It was found that both hydroxyl and sulfate radicals were generated; importantly, sulfate radicals were speculated to serve as the dominant active species in the catalytic oxidation of Acid Orange 7. In addition, a possible mechanism was proposed. This study provides new physical insights for the rational design of advanced metal-organic frameworks (MOF)-based catalysts for improved environmental remediation.

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RSC Advances · 2017 ·Vol. 7 ·期 39 ·24453-24461 · IF 3.108

Facile synthesis of Fe3O4/MIL-101 nanocomposite as an efficient heterogeneous catalyst for degradation of pollutants in Fenton-like system

Chaocheng Zhao,Pei Dong,Zongmei Liu,Guangrui Wu,Shuaijun Wang,Yongqiang Wang,Fang Liu

An active Fe3O4/MIL-101 hybrid material was prepared via a simple in situ solvothermal method and characterized as a heterogeneous Fenton-like catalyst for Rhodamine B (RhB) degradation. The Fe3O4/MIL-101 exhibited enhanced catalytic performance for RhB degradation in a neutral solution. Under optimized conditions, almost 100% removal of 10 mg L−1 RhB was achieved in 30 min using 0.5 g L−1 Fe3O4/MIL-101 and 20 mM H2O2 at initial pH 7. The reusability of Fe3O4/MIL-101 was also investigated after four runs. On the basis of the characterization of the catalyst, the results of metal leaching, the effects of radical scavengers, and hydroxyl radical (˙OH) determination, it was concluded that RhB is decomposed mainly by the attack of the hydroxyl radical (˙OH), generated by the reaction of Fe2+ species with H2O2. MIL-101 showed a significant synergistic effect with Fe3O4, in which it played the role of a solid-acid catalyst with Lewis acid sites on its surface, ensuring that a Fenton-like reaction occurred in the neutral solution.

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CHEMICAL ENGINEERING JOURNAL · 2016 · IF 5.31

Facile fabrication of Fe3O4/MIL-101(Cr) for effective removal of acid red 1 and orange G from aqueous solution

Ting Wang,Pan Zhao,Nan Lu,Hongche Chen,Conglu Zhang,Xiaohong Hou

Attractive magnetic metal-organic framework (MOF) material Fe 3 O 4 /MIL-101(Cr) (Matérial Institute Lavoisier, MIL) was synthesized by a simple reduction–precipitation method, and applied as an effective sorbent to the removal of two acid dyes, acid red 1 (AR1) and orange G (OG), in water. The novel synthetic method avoided the oxidation of Fe 2+ and made the Fe 3 O 4 /MIL-101(Cr) composite have the advantages of strong magnetism, large surface areas and excellent dispersion effect. Parameters that influenced the adsorption process, such as solution pH, adsorbent dosage, ionic strength, and so on, were investigated. Under the optimum conditions, adsorption kinetics and isotherms were determined from the obtained experimental data. The adsorption kinetics suggested the adsorption process of Fe 3 O 4 /MIL-101(Cr) toward AR1 and OG met the pseudo-second-order kinetic model. The adsorption isotherms were fitted by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Compared with the Freundlich and D–R models, the Langmuir isotherm model was found to be suitable to describe the equilibrium data, suggesting that the uptake of AR1 and OG by the Fe 3 O 4 /MIL-101(Cr) would be through monolayer adsorption. The thermodynamic results demonstrated that the adsorption was a spontaneous, exothermic and entropy decreased process. In addition, the Zeta potential data with pH value of AR1 and OG indicated that the electrostatic interactions between the dyes and the adsorbent might be critical to the adsorption mechanism. The used Fe 3 O 4 /MIL-101(Cr) could be regenerated by washing with NaOH solution and reused at least six times. The maximum adsorption capacities of the magnetic composite toward AR1 and OG were up to 142.9   mg   g −1 and 200.0   mg   g −1 , respectively. These results demonstrated that the novel composite would be an effective and easily re-usable adsorbent for AR1 and OG.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2016 · IF 8.328

Accelerated photocatalytic degradation of organic pollutant over metal-organic framework MIL-53(Fe) under visible LED light mediated by persulfate

Yaowen Gao,Simiao Li,Yixi Li,Linyu Yao,Hui Zhang

Photocatalysis based on metal-organic frameworks (MOFs) is being actively investigated as a potential technology in visible light harvesting and utilizing processes. Herein we report that MIL-53(Fe), an earth-abundant Fe-containing MOF material, shows photocatalytic activity for the degradation of Acid Orange 7 (AO7) from aqueous solution under visible LED light irradiation, yet the photocatalytic performance of bare MIL-53(Fe) was not satisfactory due to the fast recombination of photoinduced electron-hole pairs. This can be effectively overcome by adding the external electron acceptor (e.g., persulfate, PS) to the catalytic process. The accelerated photocatalytic degradation of AO7 is demonstrated by the result that the degradation efficiency of AO7 in the MIL-53(Fe)/PS/Vis process reached almost 100% within 90   min as compared to only 24% under the identical experimental conditions for the MIL-53(Fe)/Vis process. To investigate the mechanism of the MIL-53(Fe)/PS/Vis process, photoluminescence (PL) spectra, electrochemical measurements and electron paramagnetic resonance (EPR) analysis were performed. It was concluded that the efficient separation of photogenerated electrons and holes by the introduced PS and the subsequent formation of reactive radicals resulting from the activation of PS by photogenerated electrons accounted for the accelerated photocatalytic degradation of AO7 in the MIL-53(Fe)/PS/Vis process. Furthermore, the applicability of MIL-53(Fe) used in the persulfate-mediated photocatalytic process was systematically investigated in terms of the identification of reactive radicals, the reusability and stability of the photocatalyst, as well as the effect of operating parameters. The findings of this work highlighted the great potential of MOFs as photocatalysts and elucidated a new opportunity for persulfate remediation of contaminated water.

CAS / MDL: 3317-61-1
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