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Metal–Organic Frameworks with Environmental and Biomedical Applications
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Metal–Organic Frameworks with Environmental and Biomedical Applications

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (31 January 2023) | Viewed by 29221

Special Issue Editor

Dr. Constantina Papatriantafyllopoulou

E-Mail Website
Guest Editor
School of Chemistry, National University of Ireland Galway, Galway, Ireland
Interests: magnetic sensors; single-molecule magnets; multifunctional materials; metal–organic frameworks; drug carriers
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear colleagues,

Metal–organic frameworks (MOFs) have witnessed a vast development in recent years due to an intense focus on the discovery of efficient materials for technological, biomedical and environmental applications. MOFs display appealing structural features, such as high porosity, large surface area, flexible and tuneable structures, and are suitable for encapsulating a large variety of guest molecules with a wide range of applications. Among others, MOFs are suitable candidates for addressing major contemporary challenges in the environmental and biomedical fields. Concerning the latter, the use of MOFs in drug delivery, drug purification, imaging, photodynamic therapy, targeted drug therapy, etc., could improve fundamental issues in drug development and therapeutic processes. Furthermore, the application of MOFs as adsorbents and sensors for toxic species could be beneficial for environmental challenges, including the greenhouse effect, the pollution of the air and the aquatic ecosystems. This Special Issue aims to present research that focuses on the biomedical and environmental applications of MOFs, and identify and review the recent developments and breakthroughs in these fields.

Dr. Constantina Papatriantafyllopoulou
Guest Editor

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Keywords

  • Metal–organic frameworks
  • MOF
  • Drug delivery
  • Photodynamic therapy
  • Targeted drug therapy
  • Environmental applications

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Published Papers (8 papers)

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Research

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12 pages, 2985 KiB  
Article
Adsorptive Capacity, Inhibitory Activity and Processing Techniques for a Copper-MOF Based on the 3,4-Dihydroxybenzoate Ligand
by Estitxu Echenique-Errandonea, Sara Rojas, Víctor Karim Abdelkader-Fernández, Manuel Pérez-Mendoza, Ricardo F. Mendes, Paula Barbosa, Filipe Figueiredo, Flávio Figueira, Filipe A. Almeida Paz, José Manuel Delgado-López, Antonio Rodríguez-Diéguez and José Manuel Seco
Molecules 2022, 27(22), 8073; https://doi.org/10.3390/molecules27228073 - 21 Nov 2022
Cited by 3 | Viewed by 2305
Abstract
Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF—namely 1—that displays the formula [...] Read more.
Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF—namely 1—that displays the formula [Cu3L2(DMF)2]n (DMF = N,N-dimethylformamide) is described, synthesized by the combination of copper(II) and 3,4-dihydroxybenzoic acid (H3L)—both having well-known antibacterial properties. The resulting three-dimensional structure motivated us to study the antibacterial activity, adsorptive capacity and processability of the MOF in the form of pellets and membranes as a proof-of-concept to evaluate its future application in devices. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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10 pages, 2013 KiB  
Article
Surface Modification Strategy for Enhanced NO2 Capture in Metal–Organic Frameworks
by Dionysios Raptis, Charalampos Livas, George Stavroglou, Rafaela Maria Giappa, Emmanuel Tylianakis, Taxiarchis Stergiannakos and George E. Froudakis
Molecules 2022, 27(11), 3448; https://doi.org/10.3390/molecules27113448 - 26 May 2022
Cited by 6 | Viewed by 2453
Abstract
The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing [...] Read more.
The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO2 molecules. Among the functional groups considered, the highest interaction energy with NO2 (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO3H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO2 interactions (-OSO3H, -PO3H2, -OPO3H2) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO2 uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO2 uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO2 uptake performance not only in MOFs but also in various other porous materials. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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17 pages, 3948 KiB  
Article
Linker Functionalization Strategy for Water Adsorption in Metal–Organic Frameworks
by Rafaela Maria Giappa, Anastasios G. Papadopoulos, Emmanuel Klontzas, Emmanuel Tylianakis and George E. Froudakis
Molecules 2022, 27(9), 2614; https://doi.org/10.3390/molecules27092614 - 19 Apr 2022
Cited by 10 | Viewed by 2755
Abstract
Water adsorption in metal–organic frameworks has gained a lot of scientific attention recently due to the potential to be used in adsorption-based water capture. Functionalization of their organic linkers can tune water adsorption properties by increasing the hydrophilicity, thus altering the shape of [...] Read more.
Water adsorption in metal–organic frameworks has gained a lot of scientific attention recently due to the potential to be used in adsorption-based water capture. Functionalization of their organic linkers can tune water adsorption properties by increasing the hydrophilicity, thus altering the shape of the water adsorption isotherms and the overall water uptake. In this work, a large set of functional groups is screened for their interaction with water using ab initio calculations. The functional groups with the highest water affinities form two hydrogen bonds with the water molecule, acting as H-bond donor and H-bond acceptor simultaneously. Notably, the highest binding energy was calculated to be −12.7 Kcal/mol for the -OSO3H group at the RI-MP2/def2-TZVPP-level of theory, which is three times larger than the reference value. Subsequently, the effect of the functionalization strategy on the water uptake is examined on a selected set of functionalized MOF-74-III by performing Monte Carlo simulations. It was found that the specific groups can increase the hydrophilicity of the MOF and enhance the water uptake with respect to the parent MOF-74-III for relative humidity (RH) values up to 30%. The saturation water uptake exceeded 800 cm3/cm3 for all candidates, classifying them among the top performing materials for water harvesting. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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17 pages, 3906 KiB  
Article
Redox Hyperactive MOF for Li+, Na+ and Mg2+ Storage
by Hristo Rasheev, Agnieszka Seremak, Radostina Stoyanova and Alia Tadjer
Molecules 2022, 27(3), 586; https://doi.org/10.3390/molecules27030586 - 18 Jan 2022
Cited by 6 | Viewed by 2658
Abstract
To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new [...] Read more.
To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new metal-organic framework, which displays energy density exceeding that of conventional inorganic and organic electrodes, such as Li- and Na-rich oxides and anthraquinones. The designed MOF has a rhombohedral unit cell in which an Ni(II) node is coordinated by 2,5-dicyano-p-benzoquinone linkers in such a way that all components participate in the redox reaction upon lithiation, sodiation and magnesiation. The spatial and electronic changes occurring in the MOF after the interaction with Li, Na and Mg are discussed on the basis of calculated electrode potentials versus Li0/Li+, Na0/Na+ and Mg0/Mg2+, respectively. In addition, the specific capacities and energy densities are calculated and used as a measure for the electrode applicability of the designed material. Although the highest capacity and energy density are predicted for Li storage, the greater structural robustness toward Na and Mg uptake suggests a higher cycling stability in addition to lower cost. The theoretical results indicate that the MOF is a promising choice for a green electrode material (with <10% heavy metal content) and is well worth experimental testing. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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13 pages, 2124 KiB  
Article
Cinnamal Sensing and Luminescence Color Tuning in a Series of Rare-Earth Metal−Organic Frameworks with Trans-1,4-cyclohexanedicarboxylate
by Pavel A. Demakov, Alena A. Vasileva, Sergey S. Volynkin, Alexey A. Ryadun, Denis G. Samsonenko, Vladimir P. Fedin and Danil N. Dybtsev
Molecules 2021, 26(17), 5145; https://doi.org/10.3390/molecules26175145 - 25 Aug 2021
Cited by 13 | Viewed by 3357
Abstract
Three isostructural metal–organic frameworks ([Ln2(phen)2(NO3)2(chdc)2]·2DMF (Ln3+ = Y3+ for 1, Eu3+ for 2 or Tb3+ for 3; phen = 1,10-phenanthroline; H2chdc = trans-1,4-cyclohexanedicarboxylic acid) [...] Read more.
Three isostructural metal–organic frameworks ([Ln2(phen)2(NO3)2(chdc)2]·2DMF (Ln3+ = Y3+ for 1, Eu3+ for 2 or Tb3+ for 3; phen = 1,10-phenanthroline; H2chdc = trans-1,4-cyclohexanedicarboxylic acid) were synthesized and characterized. The compounds are based on a binuclear block {M2(phen)2(NO3)2(OOCR)4} assembled into a two-dime nsional square-grid network containing tetragonal channels with 26% total solvent-accessible volume. Yttrium (1)-, europium (2)- and terbium (3)-based structures emit in the blue, red and green regions, respectively, representing the basic colors of the standard RGB matrix. A doping of Eu3+ and/or Tb3+ centers into the Y3+-based phase led to mixed-metal compositions with tunable emission color and high quantum yields (QY) up to 84%. The bright luminescence of a suspension of microcrystalline 3 in DMF (QY = 78%) is effectively quenched by diluted cinnamaldehyde (cinnamal) solutions at millimolar concentrations, suggesting a convenient and analytically viable sensing method for this important chemical. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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16 pages, 1828 KiB  
Article
2D Porphyrinic Metal-Organic Frameworks Featuring Rod-Shaped Secondary Building Units
by Rory Elliott, Aoife A. Ryan, Aviral Aggarwal, Nianyong Zhu, Friedrich W. Steuber, Mathias O. Senge and Wolfgang Schmitt
Molecules 2021, 26(10), 2955; https://doi.org/10.3390/molecules26102955 - 16 May 2021
Cited by 7 | Viewed by 5641
Abstract
Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are [...] Read more.
Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are considered privileged ligands for MOF synthesis due to their tunable redox and photophysical properties. In this study, the CuII complex of 5,15-bis(4-carboxyphenyl)-10,20-diphenylporphyrin (H2L-CuII, where H2 refers to the ligand’s carboxyl H atoms) is used to prepare two new 2D porphyrinic rod MOFs PROD-1 and PROD-2. Single-crystal X-ray analysis reveals that these frameworks feature 1D MnII- or CoII-based rod-like SBUs that are coordinated by labile solvent molecules and photoactive porphyrin moieties. Both materials were characterised using infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) spectroscopy and thermogravimetric analysis (TGA). The structural attributes of PROD-1 and PROD-2 render them promising materials for future photocatalytic investigations. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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Review

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33 pages, 5242 KiB  
Review
Synthesis and Biomedical Applications of Highly Porous Metal–Organic Frameworks
by Ahmed Ahmed, Darragh McHugh and Constantina Papatriantafyllopoulou
Molecules 2022, 27(19), 6585; https://doi.org/10.3390/molecules27196585 - 5 Oct 2022
Cited by 11 | Viewed by 3271
Abstract
In this review, aspects of the synthesis, framework topologies, and biomedical applications of highly porous metal–organic frameworks are discussed. The term “highly porous metal–organic frameworks” (HPMOFs) is used to denote MOFs with a surface area larger than 4000 m2 g−1. [...] Read more.
In this review, aspects of the synthesis, framework topologies, and biomedical applications of highly porous metal–organic frameworks are discussed. The term “highly porous metal–organic frameworks” (HPMOFs) is used to denote MOFs with a surface area larger than 4000 m2 g−1. Such compounds are suitable for the encapsulation of a variety of large guest molecules, ranging from organic dyes to drugs and proteins, and hence they can address major contemporary challenges in the environmental and biomedical field. Numerous synthetic approaches towards HPMOFs have been developed and discussed herein. Attempts are made to categorise the most successful synthetic strategies; however, these are often not independent from each other, and a combination of different parameters is required to be thoroughly considered for the synthesis of stable HPMOFs. The majority of the HPMOFs in this review are of special interest not only because of their high porosity and fascinating structures, but also due to their capability to encapsulate and deliver drugs, proteins, enzymes, genes, or cells; hence, they are excellent candidates in biomedical applications that involve drug delivery, enzyme immobilisation, gene targeting, etc. The encapsulation strategies are described, and the MOFs are categorised according to the type of biomolecule they are able to encapsulate. The research field of HPMOFs has witnessed tremendous development recently. Their intriguing features and potential applications attract researchers’ interest and promise an auspicious future for this class of highly porous materials. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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18 pages, 1197 KiB  
Review
Recent Progress in Metal–Organic Framework-Derived Nanostructures in the Removal of Volatile Organic Compounds
by Deval Prasad Bhattarai, Bishweshwar Pant, Jiwan Acharya, Mira Park and Gunendra Prasad Ojha
Molecules 2021, 26(16), 4948; https://doi.org/10.3390/molecules26164948 - 16 Aug 2021
Cited by 33 | Viewed by 5511
Abstract
Air is the most crucial and life-supporting input from nature to the living beings of the planet. The composition and quality of air significantly affects human health, either directly or indirectly. The presence of some industrially released gases, small particles of anthropogenic origin, [...] Read more.
Air is the most crucial and life-supporting input from nature to the living beings of the planet. The composition and quality of air significantly affects human health, either directly or indirectly. The presence of some industrially released gases, small particles of anthropogenic origin, and the deviation from the normal composition of air from the natural condition causes air pollution. Volatile organic compounds (VOCs) are common contaminants found as indoor as well as outdoor pollutants. Such pollutants represent acute or chronic health hazards to the human physiological system. In the environment, such polluted gases may cause chemical or photochemical smog, leading to detrimental effects such as acid rain, global warming, and environmental pollution through different routes. Ultimately, this will propagate into the food web and affect the ecosystem. In this context, the efficient removal of volatile organic compounds (VOCs) from the environment remains a major threat globally, yet satisfactory strategies and auxiliary materials are far from being in place. Metal–organic frameworks (MOFs) are known as an advanced class of porous coordination polymers, a smart material constructed from the covalently bonded and highly ordered arrangements of metal nodes and polyfunctional organic linkers with an organic–inorganic hybrid nature, high porosities and surface areas, abundant metal/organic species, large pore volumes, and elegant tunability of structures and compositions, making them ideal candidates for the removal of unwanted VOCs from air. This review summarizes the fundamentals of MOFs and VOCs with recent research progress on MOF-derived nanostructures/porous materials and their composites for the efficient removal of VOCs in the air, the remaining challenges, and some prospective for future efforts. Full article
(This article belongs to the Special Issue Metal–Organic Frameworks with Environmental and Biomedical Applications)
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