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ZIF-90
SEPARATION AND PURIFICATION TECHNOLOGY · 2018 · IF 3.927

Viscosity-driven in situ self-assembly strategy to fabricate cross-linked ZIF-90/PVA hybrid membranes for ethanol dehydration via pervaporation

Zhong Wei,Qiang Liu,Chunlin Wu,Heyun Wang,Hao Wang

In this study, poly(vinyl alcohol) (PVA) hybrid membranes with zeolitic imidazolate framework-90 (ZIF-90) particles were fabricated by the viscosity-driven in situ self-assembly of ZIF-90 particles in a PVA matrix and were employed for ethanol dehydration via pervaporation (PV) technology. By this method, the size-controlled and well-distributed ZIF-90 particles were successfully embedded into PVA membranes. Based on the cross-linking reactions between the ZIF-90 particles and the PVA matrix, the ZIF-90/PVA hybrid membranes demonstrated higher mechanical strength, swelling resistance, and a high separation performance for ethanol dehydration. The ZIF-90/PVA hybrid membranes were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, a mechanical test, and water contact angle measurements. The effects of the ZIF-90 particle size, loading level, thermal treatment temperature, operation temperature, and the feed compositions of the PVA hybrid membranes on the PV performance were systematically explored. Accordingly, the hybrid membranes exhibited excellent water permeability and selectivity for water–ethanol mixture separation. Specifically, the ZIF-90/PVA hybrid membrane (M-8), which was treated thermally at 130 °C, exhibited its optimal PV performance at a flux of 268 g/(m 2 h) and a separation factor of 1379 for the PV dehydration of the 90 wt% ethanol aqueous solution at 30 °C. The ZIF-90/PVA hybrid membranes exhibited excellent potential in the PV application for ethanol dehydration.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 化学工程
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LANGMUIR · 2022 · IF 4.331

Surface Modification of Magnetic ZIF-90 Nanoparticles Improves the Microenvironment of Immobilized Lipase and Its Application in Esterification

Hongbo Suo,Xinyue Geng,Yinghui Sun,Lu Zhang,Jie Yang,Fan Yang,Hui Yan,Yi Hu,Lili Xu

Interactions of enzymes with supports significantly affect the activity and stability of immobilized enzymes. Herein, amino-functionalized ionic liquid (IL)-grafted magnetic zeolitic imidazolate framework-90 (MZIF-90) was prepared and used to immobilize porcine pancreatic lipase (PPL). The nanocomposites were fully characterized; meanwhile, the interactions between ILs and ZIF-90 were calculated based on density functional theory. The prepared biocatalyst (PPL-ILs/MZIF-90) had a lipase loading of 178.3 mg/g and hydrolysis activity up to 287.5 U/g. When the biocatalyst was used to synthesize isoamyl acetate, the reaction media, molar ratio of alcohol/acid, temperature, and reaction time were optimized. Under the optimized reaction conditions (in hexane, alcohol/acid = 3:1, under 45 °C, reacted for 9 h), the ester yield reached 85.5%. The results of the stability test showed that PPL-ILs/MZIF-90 retained 88.7% of the initial activity after storing for 35 days and 92.5% of the initial activity after reusing for seven cycles for synthesizing isoamyl acetate. Moreover, the secondary structure analysis showed that the synthesized supports protected the active conformation of immobilized lipase, which lead to the enhanced catalytic performance. Additionally, the biocatalyst can be easily separated with a magnet, which facilitated the reusability. This study provides insights regarding the application of metal organic framework composites in the field of enzyme catalysis.

CAS / MDL: 62-31-7 1116-76-3
研究领域: 生物化学 · 材料科学 · 酶工程
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Solvent-vapor-triggered crystallization of a ZIF-90 membrane with versatile separation properties towards light hydrocarbons

Xu Wang,Rui Yao,Han Zhu,Zinan Zhang,Lifeng Zhang,Qiang Ma,Hua Jin,Yanshuo Li

Membrane separation has been well acknowledged as a forward-looking technology for hydrocarbon separation. Zeolitic imidazole framework-90 (ZIF-90) with effective pore size of 5.0 Å is a promising membrane material for hydrocarbon separation. Owing to the enormous challenges facing the fabrication process, the research on the ZIF-90 polycrystalline membrane is fairly underexplored. Herein we report a solvent-vapor-triggered crystallization strategy for the production of ZIF-90 membranes. The resultant ZIF-90 membrane had a typical polycrystalline membrane structure where the regular ZIF-90 grains propagated inside the whole porous support. Intriguingly, the membrane displayed two obvious sharp cut-off regions falling between the C 3 H 6 /C 3 H 8 and n- C 4 H 10 / i- C 4 H 10 gas pairs, respectively. The ZIF-90 membrane achieved ultrafast and selective permeation of C 3 H 6 from the C 3 H 6 /C 3 H 8 mixture. The C 3 H 6 flux was about 3.4 kg·m −2 ·h −1 which was comparable to the commercial NaA zeolite membrane for organic solvent dehydration. Further, the distinctive gas transport kinetic nature enabled the ZIF-90 membranes to exclude i -C 4 H 10 and thus harvest unprecedented n -/ i -C 4 H 10 separation ability in high-temperature regions. As the temperature elevated from 25 to 150 °C, the n- C 4 H 10 permeance was enhanced from 3.0 × 10 −9 to 12 × 10 −9 mol·m −2 ·s −1 ·Pa −1 and the n- C 4 H 10 / i- C 4 H 10 separation factors was improved from 63 to 95, respectively. The high permeance and permselectivity at industrially relevant high temperatures and pressures make ZIF-90 membrane attractive for industrial light hydrocarbon separation.

CAS / MDL: 10111-08-7
研究领域: 材料科学 · 化学工程 · 膜技术
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INORGANIC CHEMISTRY · 2025 · IF 4.7

Biomineralization of Hemoglobin with ZIF-90 under Mild Conditions for Oxygen Sensing Application

Yueqin Zhang,Li Zhou,Yuexin Du,Hui Xu,Xiehaoran Zhang,Mengyao Wu,Jiaqiang Xu,Lien-Yang Chou,Junchen Chen

Hemoglobin (Hb), owing to its superior oxygen adsorption properties, has emerged as a potential material for oxygen sensing. However, the practical applications of Hb have been significantly limited due to the propensity of bioactive molecules to become deactivated. This study employed a biomineralization strategy through Metal–Organic Frameworks (MOFs), bestowing external protection to Hb in a mild aqueous system. By leveraging the intrinsic hydrophilic nature of the protein structure, we have successfully obtained the Hb@ZIF-90 composite material through the de novo synthesis method in an aqueous phase, which was applied in the field of gaseous-phase oxygen sensing. In contrast to conventional approaches, this work not only preserved the bioactivity of the Hb molecules but also improved the crystallization of the ZIF-90 shell. In addition, although the Hb size is much larger than the cages of ZIF-90, Hb can be entrapped within interstitial spaces between the ZIF crystallites; density functional theory (DFT) calculations confirmed that the encapsulation of Hb could be controlled by leveraging a competitive regulation mechanism between surfactants and hemoglobin. Moreover, the Hb@ZIF-90 composite demonstrated stable and rapid oxygen sensing capabilities in gaseous environments due to the protection from the external biomineralized shell and the presence of ordered porous channels of ZIF-90.

CAS / MDL: 25249-54-1 9003-39-8
研究领域: 材料科学 · 生物化学 · 传感技术 · 纳米技术 · 化学工程
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PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES · 2015 ·Vol. 14 ·期 9 ·1644-1650 · IF 2.267

Luminescent zinc metal—organic framework (ZIF-90) for sensing metal ions, anions and small molecules

Liu Chang,Yan Bing

We synthesize a zinc zeolite-type metal—organic framework, the zeolitic imidazolate framework (ZIF-90), which exhibits an intense blue luminescence excited under visible light. Luminescent studies indicate that ZIF-90 could be an efficient multifunctional fluorescence material for high sensitivity metal ions, anions and organic small molecules, especially for Cd 2+ , Cu 2+ , CrO 4 2− and acetone. The luminescence intensity of ZIF-90 increases with the concentration of Cd 2+ and decreases proportionally with the concentration of Cu 2+ , while the same quenched experimental phenomena appear in the sensing of CrO 4 2− . With the increase of the amount of acetone, the luminescence intensity decreases gradually in the emulsions of ZIF-90. The mechanism of the sensing properties is studied in detail as well. This study shows that ZIF-90 could be a useful luminescent sensor for metal ions, anions and organic small molecules.

研究领域: 材料科学 · 化学传感器 · 光学材料
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ChemNanoMat · 2021 ·Vol. 8 ·期 2 ·e202100389 · IF 3.154

Functionalized ZIF-90 for Gene-mediated Chemotherapy to Ameliorate Multidrug Resistance in Breast Cancer Therapy

Senyi Gong,Mengdi Shang,Dawei Li,Yanfei Cai,Jian Jin,Zhaoqi Yang

Graphical A novel nanosystem based on ZIF-90 was developed for alleviating the MDR problem .Two kinds of MB were designed to specifically hybridize with the mRNAs related to P-gp (MDR1 gene and ETS1 gene respectively). The results distinctly confirmed that the problem of MDR has been ameliorated by the designed nanosystem. Breast cancer, the most common cancer, is a threat to women's health. A great challenge for breast cancer is the multidrug resistance (MDR) problem. P-glycoprotein (P-gp) is one of main reasons to induce MDR in the therapy of breast cancer. A novel nanosystem based on ZIF-90 was developed for alleviating MDR and to improve the therapeutic efficacy. In this investigation, ZIF-90 was used as a carrier to deliver two kinds of DNA molecular beacons (MBs) and Doxorubicin (Dox). The loop sequences of two kinds of MBs were designed to specifically hybridize with the mRNAs related to P-gp (MDR1 gene and ETS1 gene, respectively), thereby directly inhibiting the expression of downstream proteins P-gp. The results of confocal fluorescence imaging and qRT-PCR analysis indicated that MB and Dox were delivered into cells and the mRNAs related to P-gp were silenced. The MTT assay showed that the IC 50 of nanosystem to the drug-resistant breast cancer cells (34.78 μg/mL) was much lower than the IC 50 of Dox to the same cells (152.7 μg/mL). These results distinctly confirmed that the problem of MDR has been ameliorated by our designed nanosystem. It is our hope that this investigation may provide a new treatment strategy for enhancing the therapeutic efficacy of chemotherapy for breast cancer.

CAS / MDL: 5970-45-6
研究领域: 癌症研究 · 纳米医学 · 分子生物学 · 化疗
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JOURNAL OF HAZARDOUS MATERIALS · 2020 · IF 9.038

A novel hybrid nanoadsorbent for effective Hg2+ adsorption based on zeolitic imidazolate framework (ZIF-90) assembled onto poly acrylic acid capped Fe3O4 nanoparticles and cysteine

Elvis Ikechukwu Nosike,Zhenqi Jiang,Lijing Miao,Ozioma Udochukwu Akakuru,Bo Yuan,Shasha Wu,Yuenan Zhang,Yujie Zhang,Aiguo Wu

This research reports a new mercury adsorbent in which Fe 3 O 4 as a core was embedded into the shell of ZIF-90 in a one-pot synthesis and the subsequent post synthesis modification (PSM) of its surface with cysteine covalently, via a Schiff’s base reaction. Poly acrylic acid (PAA) was capped on the surface of nanoparticles to prevent agglomeration of the nanoparticles. In addition, −COOH groups of PAA coordinated with Zn 2+ of ZIF-90 and this provided the platform for ZIF-90 to grow on the nanoparticles forming the core-shell structure. Based on the strong interactions between the thiol groups on the adsorbent and mercury ions as elucidated by the XPS analysis, the as-synthesized adsorbent showed selectivity for Hg 2+ . The sorbent exhibited high adsorption capacity of 900 mg g −1 towards Hg 2+ as calculated at pH 4 and the adsorption kinetics followed pseudo-second-order kinetics model better. The Hg 2+ loaded adsorbent was easily regenerated and it maintained about 70 % efficiency after the third use. Low-cost, readily available and green materials, facile preparation, efficient removal and the breakthrough in three times recyclability give the novel ZIF-90 based hybrid nanoadsorbent wide prospects in the field of environmental remediation as a good adsorbent for Hg 2+ removal in wastewater.

研究领域: 环境科学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Composite polymer electrolytes with uniform distribution of ionic liquid-grafted ZIF-90 nanofillers for high-performance solid-state Li batteries

Zhiwen Lei,Jinlai Shen,Jun Wang,Qi Qiu,Guangzhao Zhang,Shang-Sen Chi,Hongli Xu,Shuai Li,Weide Zhang,Yusheng Zhao,Yonghong Deng,Chaoyang Wang

The stable structure, high porosity and surface functionality endow metal organic frameworks (MOFs) nanoparticles as excellent nanofillers for high-performance poly (ethyleneoxide)-based solid polymer electrolytes (PEO SPEs). However, the agglomeration of MOFs severely limits their potential applications. Herein, a novel zeolitic imidazolate framework-90 nanofiller grafted with imidazole ionic liquid containing siloxane groups (ZIF-90-g-IL) is prepared by dehydration condensation reaction, which enables the uniform distribution of the nanofiller in PEO SPEs. The resulting composite PEO SPE with ZIF-90-g-IL nanofillers delivers higher ionic conductivity of 1.17 × 10 -4 S/cm at 30 °C and lithium ion transference number of 0.44, wider electrochemical stability window of 4.8 V, and stronger ability to inhibit lithium dendrite growth than the PEO SPE with unmodified ZIF-90. The strong interaction of ZIF-90-g-IL with PEO is caused by the chelation of quaternary ammonium cations of ionic liquid groups on the ZIF-90-g-IL surface with oxygen containing a lone pair of electrons of PEO, resulting in a uniform distribution of the nanofillers in PEO. The LFP||Li half cells with the PEO/ZIF-90-g-IL SPE exhibit good cycling performance with 71% capacity retention (101 mAh g −1 ) after 500 cycles at 2C under 60 °C, and show excellent cycling performance with 97.4% capacity retention (148 mAh g −1 ) after 30 cycles at 0.1C under 30 °C. The composite SPE is also used for high-voltage NCM811||Li half cells. The capacity retention is 63% (99 mAh g −1 ) after 100 cycles at 0.1C under 60 °C. The results imply ZIF-90-g-IL as effective nanofillers for SPEs showing a great potential application in all solid-state lithium metal batteries.

研究领域: 材料科学 · 能源存储
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CHEMISTRY-A EUROPEAN JOURNAL · 2024 · IF 3.9

An Efficient Bifunctional Core-Shell ZIF-90@ZIF-67 Composite as a Stable Pickering Interfacial Catalyst for the Deacetalization–Knoevenagel Tandem Reaction

Wei Liu,Yu-Qing Zhang,Zhen-Lin Dong,Zi-Xuan Chen,Lei Li,Xin-Yuan Zhao,Yang Wu,Yu-Yang Zhang

Graphical Here, the core-shell structure of ZIF-90@ZIF-67 was applied for the first time to catalyze the tandem reaction in Pickering emulsion system, which exhibited excellent catalytic performance with 99.9 % yield. Furthermore, ZIF-90@ZIF-67 has high stability and maintains good reproducibility after five cycles. This work provides a platform for the design of structurally and functionally diverse MOF-based interfacial catalysis for Pickering emulsions. Exploiting advanced solid particles is crucial to the construction of Pickering emulsions catalysis. Recently, metal-organic frameworks (MOFs) have been used as ideal emulsifiers stabilizing Pickering emulsions for interfacial catalysis. Although Pickering emulsions stabilized by core-shell MOFs have significant importance in practical studies, to date there have been very limited reports on this topic. Herein, ZIF-90@ZIF-67, a core-shell material with simultaneous acid-base bifunctionality, was synthesized by seeded epitaxial growth. It was firstly applied as an emulsifier in Pickering emulsions to catalyze the deacetalization-Knoevenagel tandem reaction, which exhibited excellent catalytic properties and achieved extremely high yields. Additionally, ZIF-90@ZIF-67 showed high stability and remained well repeatable after five cycles. This work provides a platform for the design of structurally and functionally diverse MOF-based Pickering emulsions interfacial catalysis.

研究领域: 材料科学 · 催化化学
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RSC Medicinal Chemistry · 2024 · IF 4.1

Responsive ZIF-90 nanocomposite material: targeted delivery of 10-hydroxycamptothecine to enhance the therapeutic effect of colon cancer (HCT116) cells

Ji-Chao Guo,Shi-Hui Deng,Shu-Min Zhou,Xuan Zhou,Jiajia Du,Si-Han Zhou,Qi-Hua Zhao,Zhong-Yan Cai,Xiaoxia Ren,Ming-jin Xie

There is significant value in developing multifunctional drug delivery systems with high therapeutic efficiency for diagnosing and treating tumors. In this study, we synthesized the ATP-triggered and pH-sensitive material ZIF-90 using the liquid-phase diffusion method. This was done to load 10-hydroxycamptothecin (HCPT), and the FA-PEG-NH2 conjugate was synthesized through an amidation reaction. We further modified the HCPT@ZIF-90 nanocomposite by employing the Schiff base reaction to create the HCPT@ZIF-90-PEG-FA nanomaterial. Drug loading test results revealed a high HCPT drug loading of up to 22.3% by weight. In the drug release experiment, the cumulative drug release of HCPT@ZIF-90 nanomaterials in pH 5.4 and ATP solutions was the highest after 72 hours. The active targeted delivery of FA and the dual-responsive release of HCPT by ZIF-90 significantly enhanced the therapeutic effect of HCPT@ZIF-90-PEG-FA on human colon cancer cells (HCT116). In the cytotoxicity test, when 100 μg mL−1 of HCPT@ZIF-90-PEG-FA was incubated with cells, the cell survival rate was 16.61 ± 1.19%, significantly lower than that of the other experimental groups. This result indicates that HCPT@ZIF-90-PEG-FA exhibits excellent anti-tumor activity. Cell cycle experiments have shown that HCPT@ZIF-90-PEG-FA may inhibit the proliferation of cancer cells by blocking DNA synthesis and halting cell cycle progression. Cell uptake experiments showed that HCPT@ZIF-90-PEG-FA was mainly present in the cytoplasm of HCT1116 cells, indicating successful cellular entry of the drug to exert its therapeutic effect. In vivo experiments also demonstrated that HCPT@ZIF-90-PEG-FA nanomaterials can effectively eradicate HCT116 tumors. The utilization of the nano-drug carrier ZIF-90, along with the modification with PEG-FA, notably improved the therapeutic efficacy of HCPT. These results suggest that the system, with its active targeted delivery of FA and dual-responsive release of HCPT, could present a novel strategy for treating human colorectal cancer.

研究领域: 药学 · 肿瘤学 · 纳米医学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Room-temperature synthesis of hydrophobic/oleophilic ZIF-90-CF3/melamine foam composite for the efficient removal of organic compounds from wastewater

Xufei Li,Baoyou Yan,Weiqiu Huang,Hui Bian,Xinya Wang,Jiahui Zhu,Shaocan Dong,Yuyu Wang,Weihua Chen

To overcome the shortage of conventional synthetic methods, such as long reaction time at high temperature and pressure (HTP) or poor performance at room temperature and pressure (RTP), a facile and economical strategy was employed to prepare high-performance ZIF-90 for the first time at RTP only by adding triethylamine (TEA). Herein, we successfully prepared ZIF-90 nanocrystals by a two-step stirring method within several minutes (5–30 min) and their structure parameters (e.g., BET surface areas, 916–1235 m 2 ·g −1 ) were also tuned simultaneously, which were much better than reported samples prepared at RTP. Afterwards, by changing functional ligands, hydrophobic ZIF-90-CF 3 with low surface energy was also designed. With the ligand side of aldehyde (–CHO) and trifluoromethyl (-CF 3 ) groups on ZIF-90 and ZIF-90-CF 3 , the water vapor uptakes and adsorption heats decreased from 7.9 to 0.79 mmol·g −1 and 20.6 to 2.6 kJ·mmol −1 , respectively. Additionally, a shaped ZIF-90-CF 3 /melamine foam (MF) composite with both hydrophobic and oleophilic properties exhibited extraordinary organic compounds (OCs)-water separation ability, including a high adsorption capacity (40.1–108.7 g‧g −1 ) towards various OCs. Furthermore, owing to its excellent compressibility and mechanical stability, the ZIF-90-CF 3 /MF composite can be regenerated by slightly squeezing the adsorbed OCs, indicating the potential for possible commercialisation of the derived MOF/MF composites for the efficient purification of wastewater.

CAS / MDL: 1320-06-5
研究领域: 材料科学 · 环境工程 · 化学工程
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ACS Applied Nano Materials · 2021 · IF 5.097

(3-Aminopropyl) Triethoxysilane-Modified ZIF-90 Nanoparticle/Polydimethylsiloxane Mixed Matrix Membranes for Ethanol Recovery via Pervaporation

Zhentong Han,Yaxin Zhao,Haoji Jiang,Ao Sheng,Hao Li,Hao Jia,Zhiyuan Yun,Zhong Wei,Heyun Wang

The present study eliminated nonselective defects by amending the MOF-based mixed matrix membrane (MMM) interface with (3-aminopropyl) triethoxysilane (APTES) via Schiff’s base reaction. This modification on the ZIF-90 nanoparticle surfaces enhanced the polydimethylsiloxane (PDMS) matrix interaction in the MMMs. Interfacial defects were then minimized through APTES-ZIF-90 nanoparticle surface alkoxy and PDMS chain hydroxyl group cross-linking. Enhanced chemical interactions between the nanoparticles and the polymeric matrix in the APTES-ZIF-90/PDMS MMMs resulted in higher interface compatibility and separation performance than the ZIF-90 nanoparticle MMMs, which ultimately improved its ethanol affinity and hydrophobicity. When the load of APTES-ZIF-90 nanoparticles was 15% and the temperature was 40 °C, the pervaporation performance of APTES-ZIF-90/PDMS MMMs was optimal, the separation factor was 16.8, and the permeation flux was 223 g/(m2·h). Compared with pure PDMS, the separation factor and permeation flux increased by 91 and 67%, respectively. In addition, stable APTES-ZIF-90/PDMS MMM pervaporation performance was observed after an optimal operation time of 120 h. Overall, the present work presented methods to optimize MOF-based MMMs for enhanced interface morphology and separation performance for ethanol recovery.

研究领域: 材料科学 · 分离技术
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