Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Inorganic Materials and Metal-Organic Frameworks".

Deadline for manuscript submissions: 31 December 2024 | Viewed by 19346

Special Issue Editors

School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, China
Interests: metal–organic frameworks; porous materials; fluorescent sensors; environmental sustainability; photocatalysis
School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, China
Interests: metal–organic frameworks; coordination chemistry; sensors; photocatalysis; gas capture

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Guest Editor
School of Environmental and Chemical Engineering, Shanghai University, Shanghai, China
Interests: porous coordination polymers; energy storage; gas storage; photocatalysis; electrocatalysis

Special Issue Information

Dear Colleagues,

Metal–organic frameworks (MOFs , also known as porous coordination polymers or PCPs) are formed through the assembly of metal ions or clusters and organic linkers, giving rise to crystalline structures with an open framework and significant porous texture development. The frameworks have excellent designability, regulatability, and modifiability in terms of their composition, topology, pore size, and surface chemistry, thus making them suitable candidates for various applications. Currently, MOFs are still attracting significant interest from researchers across disciplines including chemistry, materials science, and engineering. The outstanding structural diversity and precise controllability of MOF structures have endowed them with incredible fucntions that are able to address many enduring societal challenges pertaining to energy and environmental sustainability.

This Special Issue of Nanomaterials focuses on the field of synthesis and the characterization of MOFs and MOF-based micro/nanoscale materials for advanced applications, including, but not limited to, gas storage/capture, chemical sensing, photoelectrocatalysis, pollutant adsorption and degradation, organic transformation, drug delivery, and so on.

I hope that this Special Issue will uncover deep insights into MOF micro/nanoscale materials and enhance communication among scientists around the world. Original research articles, communications, and reviews are all welcome.

Dr. Jian Wang
Dr. Pengyan Wu
Dr. Wenqian Chen
Guest Editors

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Keywords

  • metal–organic frameworks
  • porous materials
  • sensor
  • photocatalysis/ catalysis
  • energy storage
  • gas storage/capture

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Published Papers (11 papers)

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Research

16 pages, 4681 KiB  
Article
M-Doped (M = Zn, Mn, Ni) Co-MOF-Derived Transition Metal Oxide Nanosheets on Carbon Fibers for Energy Storage Applications
by Andrés González-Banciella, David Martinez-Diaz, Adrián de Hita, María Sánchez and Alejandro Ureña
Nanomaterials 2024, 14(22), 1846; https://doi.org/10.3390/nano14221846 - 19 Nov 2024
Viewed by 346
Abstract
Carbon fiber, with its strong mechanical properties and electrical conductivity, is ideal as a fiber electrode in wearable or structural energy storage devices. However, its energy storage capacity is limited, and coatings like transition metal oxides (TMOs) enhance its electrochemical performance. Metal–organic frameworks [...] Read more.
Carbon fiber, with its strong mechanical properties and electrical conductivity, is ideal as a fiber electrode in wearable or structural energy storage devices. However, its energy storage capacity is limited, and coatings like transition metal oxides (TMOs) enhance its electrochemical performance. Metal–organic frameworks (MOFs) are commonly used to grow TMOs on carbon fibers, increasing the surface area for better energy storage. Despite this, TMOs have limited electrical conductivity, so ion exchange is often used to dope them with additional cations, improving both conductivity and energy storage capacity. This study compares different ion-exchange cations in ZIF-L-derived TMO coatings on carbon fiber. Testing both supercapacitor and Li-ion battery applications, Ni-doped samples showed superior results, attributed to their higher exchange ratio with cobalt. As a supercapacitor electrode, the Ni-doped material achieved 13.3 F/g at 50 mA/g—66% higher than undoped samples. For Li-ion battery anodes, it reached a specific capacity of 410.5 mAh/g at 25 mA/g, outperforming undoped samples by 21.4%. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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22 pages, 5018 KiB  
Article
Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation
by Marvin Kloß, Lara Schäfers, Zhenyu Zhao, Christian Weinberger, Hans Egold and Michael Tiemann
Nanomaterials 2024, 14(22), 1791; https://doi.org/10.3390/nano14221791 - 7 Nov 2024
Viewed by 595
Abstract
Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential [...] Read more.
Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential to modify the size of its one-dimensional pore channels and the hydrophobicity of pore walls using various linker ligands during synthesis. Thermal activation of these materials yields accessible open metal sites (i.e., under-coordinated metal centers) at the pore walls, thus acting as strong primary binding sites for guest molecules, including water. We study the effect of the pore size and linker hydrophobicity within a series of Ni2+-based isoreticular frameworks (i.e., Ni2L, L = dhtp, dhip, dondc, bpp, bpm, tpp), analyzing their water sorption behavior and the water interactions in the confined pore space. For this purpose, we apply water vapor sorption analysis and Fourier transform infrared spectroscopy. In addition, defect degrees of all compounds are determined by thermogravimetric analysis and solution 1H nuclear magnetic resonance spectroscopy. We find that larger defect degrees affect the preferential sorption sites in Ni2dhtp, while no such indication is found for the other materials in our study. Instead, strong evidence is found for the formation of water bridges/chains between coordinating water molecules, as previously observed for hydrophobic porous carbons and mesoporous silica. This suggests similar sorption energies for additional water molecules in materials with larger pore sizes after saturation of the primary binding sites, resulting in more bulk-like water arrangements. Consequently, the sorption mechanism is driven by classical pore condensation through H-bonding anchor sites instead of sorption at discrete sites. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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16 pages, 3182 KiB  
Article
Data-Driven and Machine Learning to Screen Metal–Organic Frameworks for the Efficient Separation of Methane
by Yafang Guan, Xiaoshan Huang, Fangyi Xu, Wenfei Wang, Huilin Li, Lingtao Gong, Yue Zhao, Shuya Guo, Hong Liang and Zhiwei Qiao
Nanomaterials 2024, 14(13), 1074; https://doi.org/10.3390/nano14131074 - 24 Jun 2024
Viewed by 1205
Abstract
With the rapid growth of the economy, people are increasingly reliant on energy sources. However, in recent years, the energy crisis has gradually intensified. As a clean energy source, methane has garnered widespread attention for its development and utilization. This study employed both [...] Read more.
With the rapid growth of the economy, people are increasingly reliant on energy sources. However, in recent years, the energy crisis has gradually intensified. As a clean energy source, methane has garnered widespread attention for its development and utilization. This study employed both large-scale computational screening and machine learning to investigate the adsorption and diffusion properties of thousands of metal–organic frameworks (MOFs) in six gas binary mixtures of CH4 (H2/CH4, N2/CH4, O2/CH4, CO2/CH4, H2S/CH4, He/CH4) for methane purification. Firstly, a univariate analysis was conducted to discuss the relationships between the performance indicators of adsorbents and their characteristic descriptors. Subsequently, four machine learning methods were utilized to predict the diffusivity/selectivity of gas, with the light gradient boosting machine (LGBM) algorithm emerging as the optimal one, yielding R2 values of 0.954 for the diffusivity and 0.931 for the selectivity. Furthermore, the LGBM algorithm was combined with the SHapley Additive exPlanation (SHAP) technique to quantitatively analyze the relative importance of each MOF descriptor, revealing that the pore limiting diameter (PLD) was the most critical structural descriptor affecting molecular diffusivity. Finally, for each system of CH4 mixture, three high-performance MOFs were identified, and the commonalities among high-performance MOFs were analyzed, leading to the proposals of three design principles involving changes only to the metal centers, organic linkers, or topological structures. Thus, this work reveals microscopic insights into the separation mechanisms of CH4 from different binary mixtures in MOFs. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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19 pages, 7370 KiB  
Article
Enhancing the Green Synthesis of Glycerol Carbonate: Carboxylation of Glycerol with CO2 Catalyzed by Metal Nanoparticles Encapsulated in Cerium Metal–Organic Frameworks
by Simon Lukato, Michał Wójcik, Agnieszka Krogul-Sobczak and Grzegorz Litwinienko
Nanomaterials 2024, 14(8), 650; https://doi.org/10.3390/nano14080650 - 9 Apr 2024
Viewed by 1246
Abstract
The reaction of glycerol with CO2 to produce glycerol carbonate was performed successfully in the presence of gold nanoparticles (AuNPs) supported by a metal–organic framework (MOF) constructed from mixed carboxylate (terephthalic acid and 1,3,5-benzenetricarboxylic acid). The most efficient were two AuNPs@MOF catalysts [...] Read more.
The reaction of glycerol with CO2 to produce glycerol carbonate was performed successfully in the presence of gold nanoparticles (AuNPs) supported by a metal–organic framework (MOF) constructed from mixed carboxylate (terephthalic acid and 1,3,5-benzenetricarboxylic acid). The most efficient were two AuNPs@MOF catalysts prepared from pre-synthesized MOF impregnated with Au3+ salt and subsequently reduced to AuNPs using H2 (catalyst 4%Au(H2)@MOF1) or reduced with NaBH4 (catalyst 4%Au@PEI-MOF1). Compared to existing catalysts, AuNPs@MOFs require simple preparation and operate under mild and sustainable conditions, i.e., a much lower temperature and the lowest CO2 overpressure ever reported, with MgCO3 having been found to be the optimal dehydrating agent. Although the yield of the process is still not competitive with previously developed systems, the most promising advantage is the highest TOF (78 h−1) ever reported for this reaction. The optimal parameters observed for AuNPs were also tested on AgNPs and CuNPs with promising results, suggesting their great potential for industrial application. The catalysts were characterized by XRD, TEM, SEM-EDS, ICP-MS, XPS, and porosity measurements, confirming that AuNPs are present in low concentration, uniformly distributed, and confined to the cavities of the MOF. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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13 pages, 4722 KiB  
Communication
Stability of Zr-Based UiO-66 Metal–Organic Frameworks in Basic Solutions
by Jun Yeong Kim, Jiwon Kang, Seungheon Cha, Haein Kim, Dopil Kim, Houng Kang, Isaac Choi and Min Kim
Nanomaterials 2024, 14(1), 110; https://doi.org/10.3390/nano14010110 - 2 Jan 2024
Cited by 8 | Viewed by 3200
Abstract
Although Zr-based metal–organic frameworks (MOFs) exhibit robust chemical and physical stability in the presence of moisture and acidic conditions, their susceptibility to nucleophilic attacks from bases poses a critical challenge to their overall stability. Herein, we systematically investigate the stability of Zr-based UiO-66 [...] Read more.
Although Zr-based metal–organic frameworks (MOFs) exhibit robust chemical and physical stability in the presence of moisture and acidic conditions, their susceptibility to nucleophilic attacks from bases poses a critical challenge to their overall stability. Herein, we systematically investigate the stability of Zr-based UiO-66 (UiO = University of Oslo) MOFs in basic solutions. The impact of 11 standard bases, including inorganic salts and organic bases, on the stability of these MOFs is examined. The destruction of the framework is confirmed through powder X-ray diffraction (PXRD) patterns, and the monitored dissolution of ligands from the framework is assessed using nuclear magnetic resonance (NMR) spectroscopy. Our key findings reveal a direct correlation between the strength and concentration of the base and the destruction of the MOFs. The summarized data provide valuable insights that can guide the practical application of Zr-based UiO-66 MOFs under basic conditions, offering essential information for their optimal utilization in various settings. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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12 pages, 7549 KiB  
Article
Bismuth-Based Metal–Organic Framework as a Chemiresistive Sensor for Acetone Gas Detection
by Ashraf Ali, Yaser E. Greish, Reem H. Alzard, Lamia A. Siddig, Ahmed Alzamly, Naser Qamhieh and Saleh T. Mahmoud
Nanomaterials 2023, 13(23), 3041; https://doi.org/10.3390/nano13233041 - 28 Nov 2023
Cited by 4 | Viewed by 1400
Abstract
Analyzing acetone in the exhaled breath as a biomarker has proved to be a non-invasive method to detect diabetes in humans with good accuracy. In this work, a Bi-gallate MOF doped into a chitosan (CS) matrix containing an ionic liquid (IL) was fabricated [...] Read more.
Analyzing acetone in the exhaled breath as a biomarker has proved to be a non-invasive method to detect diabetes in humans with good accuracy. In this work, a Bi-gallate MOF doped into a chitosan (CS) matrix containing an ionic liquid (IL) was fabricated to detect acetone gas with a low detection limit of 10 ppm at an operating temperature of 60 °C and 5 V operating bias. The sensor recorded the highest response to acetone in comparison to other test gases, proving its high selectivity along with long-term stability and repeatability. The sensor also exhibited ultra-fast response and recovery times of 15 ± 0.25 s and 3 ± 0.1 s, respectively. Moreover, the sensor membrane also exhibited flexibility and ease of fabrication, making it ideal to be employed as a real-time breath analyzer. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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13 pages, 2962 KiB  
Article
Tuning Electromagnetic Parameters Induced by Synergistic Dual-Polarization Enhancement Mechanisms with Amorphous Cobalt Phosphide with Phosphorus Vacancies for Excellent Electromagnetic Wave Dissipation Performance
by Bo Wen, Yunzi Miao, Zhijie Zhang, Na Li, Jiyuan Xiao, Yushuo Li, Jiangtao Feng, Shujiang Ding and Guorui Yang
Nanomaterials 2023, 13(23), 3025; https://doi.org/10.3390/nano13233025 - 27 Nov 2023
Viewed by 1204
Abstract
The understanding of amorphous and heterojunction materials has been widely used in the field of electromagnetic wave absorption due to their unique physical and chemical properties. However, the effectiveness of individual strategies currently used is still limited. Well-designed compositions and amorphous structures simplify [...] Read more.
The understanding of amorphous and heterojunction materials has been widely used in the field of electromagnetic wave absorption due to their unique physical and chemical properties. However, the effectiveness of individual strategies currently used is still limited. Well-designed compositions and amorphous structures simplify the effect of different polarization mechanisms on the absorption of electromagnetic waves. In this work, through the carbonization and controlled phosphating of one-dimensional Co Metal–Organic Framework (Co-MOF) nanorods, the synthesis of complex components and amorphous CoPx with phosphorus vacancies is successfully accomplished, thus adjusting the optimization of electromagnetic parameters. Phosphorus-vacancy-induced defective polarization loss and enhanced-electronegativity-differences-induced dipole polarization loss synergistically as a dual-polarization strategy significantly improved the electromagnetic parameters and impedance matching. In conclusion, the electromagnetic parameters of the Co@CoPx@C composites are indeed significantly regulated, with reflection losses of −55 dB and a bandwidth of up to 5.5 GHz. These innovative research ideas provide instructive thinking for the development of amorphous absorbers with vacancies. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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12 pages, 32369 KiB  
Article
Post-Synthetic Modification of an Amino-Functionalized Metal–Organic Framework for Highly In Situ Luminescent Detection of Mercury (II)
by Chen Ji, Li Pei, Junyi Qin, Pengyan Wu, Nuo Su, Ting Zhang, Yexin Zhang and Jian Wang
Nanomaterials 2023, 13(20), 2784; https://doi.org/10.3390/nano13202784 - 17 Oct 2023
Viewed by 1202
Abstract
A sulfur-containing metal–organic framework, donated as UiO-66-NSMe, was prepared by the post-synthetic modification (PSM) of UiO-66-NH2 with 2-(Methylthio)benzaldehyde, and the successful synthesis of PSM was confirmed by X-ray photoelectron spectroscopy (XPS), FT-IR and 1H NMR studies. According to the characteristics of [...] Read more.
A sulfur-containing metal–organic framework, donated as UiO-66-NSMe, was prepared by the post-synthetic modification (PSM) of UiO-66-NH2 with 2-(Methylthio)benzaldehyde, and the successful synthesis of PSM was confirmed by X-ray photoelectron spectroscopy (XPS), FT-IR and 1H NMR studies. According to the characteristics of mercury thiophilic, UiO-66-NSMe could be used as a luminescent sensor for Hg2+ detection with a high selectivity and sensitivity (Ksv = 2.5 × 104 M−1; LOD = 20 nM), which could be attributed to the coordination between sulfur sites and Hg2+ based on XPS results. In practical applications, UiO-66-NSMe yielded satisfactory recovery rates (ranging from 96.1% to 99.5%) when it was employed for detecting Hg2+ in spiked environmental samples. Furthermore, UiO-66-NSMe was successfully employed to detect mercury (II) residues with the in situ rapid nondestructive imaging in simulated fresh agricultural products. Thus, this PSM strategy could provide good guidance for environmental protection methodologies in the future. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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14 pages, 15493 KiB  
Article
Specific Recognition and Adsorption of Volatile Organic Compounds by Using MIL-125-Based Porous Fluorescence Probe Material
by Qiuyu Wu, Feiyang Tian, Wenqian Chen, Jianying Wang and Bo Lei
Nanomaterials 2023, 13(19), 2732; https://doi.org/10.3390/nano13192732 - 9 Oct 2023
Cited by 2 | Viewed by 1426
Abstract
The severity of the volatile organic compounds (VOCs) issue calls for effective detection and management of VOC materials. Metal-organic frameworks (MOFs) are organic-inorganic hybrid crystals with promising prospects in luminescent sensing for VOC detection and identification. However, MOFs have limitations, including weak response [...] Read more.
The severity of the volatile organic compounds (VOCs) issue calls for effective detection and management of VOC materials. Metal-organic frameworks (MOFs) are organic-inorganic hybrid crystals with promising prospects in luminescent sensing for VOC detection and identification. However, MOFs have limitations, including weak response signals and poor sensitivity towards VOCs, limiting their application to specific types of VOC gases. To address the issue of limited recognition and single luminosity for specific VOCs, we have introduced fluorescent guest molecules into MOFs as reference emission centers to enhance sensitivity. This composite material combines the gas adsorption ability of MOFs to effectively adsorb VOCs. We utilized (MIL-125/NH2-MIL-125) as the parent material for adsorbing fluorescent molecules and selected suitable solid fluorescent probes (FGFL-B1) through fluorescence enhancement using thioflavin T and MIL-125. FGFL-B1 exhibited a heightened fluorescence response to various VOCs through charge transfer between fluorescent guest molecules and ligands. The fluorescence enhancement effect of FGFL-B1 on tetrahydrofuran (THF) was particularly pronounced, accompanied by a color change from yellow to yellowish green in the presence of CCl4. FGFL-B1 demonstrated excellent adsorption properties for THF and CCl4, with saturated adsorption capacities of 655.4 mg g−1 and 811.2 mg g−1, respectively. Furthermore, FGFL-B1 displayed strong luminescence stability and reusability, making it an excellent sensing candidate. This study addresses the limitations of MOFs in VOC detection, opening avenues for industrial and environmental applications. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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21 pages, 5449 KiB  
Article
Synthesis of Aluminum-Based Metal–Organic Framework (MOF)-Derived Carbon Nanomaterials and Their Water Adsorption Isotherm
by Dasom Jeong, Seong Cheon Kim, Taeseop An, Dongho Lee, Haejin Hwang, Siyoung Q. Choi and Jeasung Park
Nanomaterials 2023, 13(16), 2351; https://doi.org/10.3390/nano13162351 - 16 Aug 2023
Cited by 1 | Viewed by 2623
Abstract
The characteristics of water vapor adsorption depend on the structure, porosity, and functional groups of the material. Metal–organic framework (MOF)-derived carbon (MDC) is a novel material that exhibits a high specific area and tunable pore sizes by exploiting the stable structure and porosity [...] Read more.
The characteristics of water vapor adsorption depend on the structure, porosity, and functional groups of the material. Metal–organic framework (MOF)-derived carbon (MDC) is a novel material that exhibits a high specific area and tunable pore sizes by exploiting the stable structure and porosity of pure MOF materials. Herein, two types of aluminum-based MOFs were used as precursors to synthesize hydrophobic microporous C-MDC and micro-mesoporous A-MDC via carbonization and activation depending on the type of ligands in the precursors. C-MDC and A-MDC have different pore characteristics and exhibit distinct water adsorption properties. C-MDC with hydrophobic properties and micropores exhibited negligible water adsorption (108.54 mgg−1) at relatively low pressures (P/P0~0.3) but showed a rapid increase in water adsorption ability (475.7 mgg−1) at relative pressures of about 0.6. A comparison with the isotherm model indicated that the results were consistent with the theories, which include site filling at low relative pressure and pore filling at high relative pressure. In particular, the Do–Do model specialized for type 5 showed excellent agreement. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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23 pages, 36653 KiB  
Article
Zeolitic Imidazolate Framework-8 (ZIF-8) as a Drug Delivery Vehicle for the Transport and Release of Telomerase Inhibitor BIBR 1532
by Shunyu Zhang, Jinxia Li, Liang Yan, Yue You, Feng Zhao, Jixing Cheng, Limin Yang, Yanqi Sun, Qingchao Chang, Ru Liu and Yunhui Li
Nanomaterials 2023, 13(11), 1779; https://doi.org/10.3390/nano13111779 - 31 May 2023
Cited by 11 | Viewed by 3959
Abstract
Telomerase is constitutively overexpressed in the majority of human cancers and telomerase inhibition provides a promising broad-spectrum anticancer therapeutic strategy. BIBR 1532 is a well-known synthetic telomerase inhibitor that blocks the enzymatic activity of hTERT, the catalytic subunit of telomerase. However, water insolubility [...] Read more.
Telomerase is constitutively overexpressed in the majority of human cancers and telomerase inhibition provides a promising broad-spectrum anticancer therapeutic strategy. BIBR 1532 is a well-known synthetic telomerase inhibitor that blocks the enzymatic activity of hTERT, the catalytic subunit of telomerase. However, water insolubility of BIBR 1532 leads to low cellular uptake and inadequate delivery and thus, limits its anti-tumor effects. Zeolitic imidazolate framework-8 (ZIF-8) is considered as an attractive drug delivery vehicle for improved transport, release and anti-tumor effects of BIBR 1532. Herein, ZIF-8 and BIBR 1532@ZIF-8 were synthesized, respectively, and the physicochemical characterizations confirmed the successful encapsulation of BIBR 1532 in ZIF-8 coupled with an improved stability of BIBR 1532. ZIF-8 could alter the permeability of lysosomal membrane probably by the imidazole ring-dependent protonation. Moreover, ZIF-8 encapsulation facilitated the cellular uptake and release of BIBR 1532 with more accumulation in the nucleus. BIBR 1532 encapsulation with ZIF-8 triggered a more obvious growth inhibition of cancer cells as compared with free BIBR 1532. A more potent inhibition on hTERT mRNA expression, aggravated G0/G1 arrest accompanied with an increased cellular senescence were detected in BIBR 1532@ZIF-8-treated cancer cells. Our work has provided preliminary information on improving the transport, release and efficacy of water-insoluble small molecule drugs by using ZIF-8 as a delivery vehicle. Full article
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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