Metal-organic Frameworks Research Articles

Empowering DNA-Based Information Processing: Computation and Data Storage.

Information processing is a critical topic in the digital age, as silicon-based circuits face unprecedented challenges such as data explosion, immense energy consumption, and approaching physical limits. Deoxyribonucleic acid (DNA), naturally selected as a carrier for storing and using genetic information, possesses unique advantages for information processing, which has given rise to the emerging fields of DNA computing and DNA data storage. To meet the growing practical demands, a wide variety of materials and interfaces have been introduced into DNA information processing technologies, leading to significant advancements. This review summarizes the advances in materials and interfaces that facilitate DNA computation and DNA data storage. We begin with a brief overview of the fundamental functions and principles of DNA computation and DNA data storage. Subsequently, we delve into DNA computing systems based on various materials and interfaces, including microbeads, nanomaterials, DNA nanostructures, hydrophilic-hydrophobic compartmentalization, hydrogels, metal-organic frameworks, and microfluidics. We also explore DNA data storage systems, encompassing encapsulation materials, microfluidics techniques, DNA nanostructures, and living cells. Finally, we discuss the current bottlenecks and obstacles in the fields and provide insights into potential future developments.

Cadmium(II)-Organic Frameworks with the Polynuclear Unit: Dimensionality Control and Luminescence Response to Pyridine

New porous metal-organic frameworks (MOF) [Cd7(Btdc)7(Bpa)2(Dmf)2(H2O)2] · 15Dmf · 2H2O (I) and [Cd7(Btdc)7(Bpe)2(Dmf)2] · 15Dmf · 3H2O (II) (H2Btdc is 2,2’-bithiophene-5,5’-dicarboxylic acid, Bpa is 1,2-bis(4-pyridyl)ethane, Bpe is 1,2-bis(4-pyridyl)ethylene, and Dmf is N,N-dimethylformamide) are synthesized under solvatothermal conditions. The structures and compositions of the compounds are determined by single-crystal X-ray diffraction (XRD) (CIF files ССDС nos. 2364290 (I) and 2364289 (II)) and confirmed by powder XRD, elemental analysis, thermogravimetry, and IR spectroscopy. Compound I has a 2D structure based on the heptanuclear discrete building unit {Cd7} with the linear structure. Compound II is a 3D MOF in which the {Cd7} building units are linked into a continuous chain motif due to additional interactions. The formation of discrete or continuous chains is directly related to the nature of the N-donor bridging ligand (Bpe or Bpa). Compounds I and II have open structures with the accessible volume about 50%. The solvate molecules are replaced by thiophene, benzene, and pyridine, and the luminescence properties of the prepared adducts are studied. Luminescence quenching in the presence of thiophene and an increase in the luminescence intensity in the presence of pyridine accompanied by a change in the quantum yield by 4–5 times are shown.

Cerium-Doped, Alendronate-Loaded, Metal–Organic Framework Nanodrug for Delayed Osteoporosis Progress

Cerium-Doped, Alendronate-Loaded, Metal–Organic Framework Nanodrug for Delayed Osteoporosis Progress

Development of the Cluster Chemistry, Supramolecular Chemistry and Chemistry of Metal-Organic Frameworks by Professor Vladimir P. Fedin and His School

The article briefly summarizes the main scientific directions contributed to and developed by the outstanding scientist—a leader in the field of coordination chemistry, cluster chemistry, supramolecular chemistry and chemistry of metal-organic coordination polymers, Corresponding Member of the Russian Academy of Sciences Vladimir Petrovich Fedin.

Mn and Zn-Doped Multivariate Metal-Organic Framework as a Metalloimmunological Adjuvant to Promote Protection Against Tuberculosis Infection.

A first-in-class vaccine adjuvant delivery system, Mn-ZIF, is developed by incorporating manganese (Mn) into the zinc-containing zeolitic-imidazolate framework-8 (ZIF-8). The mixed metal approach, which allowed for tunable Mn doping, is made possible by including a mild reducing agent in the reaction mixture. This approach allows up to 50% Mn, with the remaining 50% Zn within the ZIF. This multivariate approach exhibits significantly decreased cytotoxicity compared to ZIF-8. The porous structure of Mn-ZIF enables the co-delivery of the STING agonist cyclic di-adenosine monophosphate (CDA) through post-synthetic loading, forming CDA@Mn-ZIF. The composite demonstrated enhanced cellular uptake and synergistic activation of the cGAS-STING pathway, producing proinflammatory cytokines and activating antigen-presenting cells (APCs). In a preclinical Mycobacterium tuberculosis (Mtb) model, CDA@Mn-ZIF formulates with the CysVac2 fusion protein elicited a potent antigen-specific T-cell response and significantly reduced the mycobacterial burden in the lungs of infected mice. These findings highlight the potential of CDA@Mn-ZIF as a promising adjuvant for subunit vaccines, offering a novel approach to enhancing vaccine efficacy and protection against infectious diseases such as tuberculosis.

Recent Advances of Photocatalytic CO2 Reduction Based on Hybrid Molecular Catalyst/Semiconductor Photocatalysts: A Review.

Molecular catalysts often exhibit superior activity and selectivity in the process of photocatalytic reduction of CO2 (PCR). However, the practical application of molecular catalysts is restricted by the unsatisfied charge separation, low stability, and recycling difficulty. Fortunately, constructing organic-inorganic hybrids of molecular catalysts and semiconductors can tackle the above problems, which can improve the efficiency of charge separation and keep beneficial active sites simultaneously. However, there is no comprehensive review of the state-of-the-art of the molecular catalyst/semiconductor hybrids. Herein, the present advances and challenges of the molecular catalyst/semiconductor hybrids for PCR application are outlined. Specifically, the review is summarized by the composition of semiconductors adopted to form the hybrids with molecular catalysts, including metal oxide, carbon nitride (CN), graphene, quantum dots, sulfides, layered double hydroxides (LDH), molecular complexes, and so on. The review presented here is expected to guide the design of efficient inorganic-organic composites for solar energy conversion.

Ultrafast synthesis and binder‐free fabrication of a monolithic metal–organic framework for efficient carbon capture

AbstractAchieving rapid synthesis alongside efficient shaping without sacrificing high porosity and crystallinity poses significant challenges for metal–organic frameworks (MOFs) in practical applications. Here, we report an ultrafast, scalable method for preparing an ultramicroporous MOF at room temperature. This method achieves a space–time yield significantly higher than conventional MOF synthesis by orders of magnitude. As a result of strongly promoted crystal nucleation by careful selection of solvent and metal source, the MOF material is produced in a gel state offering both high crystallinity and processability. This allows for the binder‐free fabrication of monolithic adsorbents with predesigned macro shapes and sizes. Owing to its narrowly distributed pore size and high‐density open metal sites, the monolithic adsorbent demonstrates top‐tier selectivity for CO2/N2 (>200) and CO2/CH4 separations. The performance sets a new benchmark among current MOF xero‐ or aerogel monoliths. Breakthrough experiments further verify its robust ability for carbon capture under dynamic conditions.

Bifunctional MOFs Nanozyme with Peroxidase Activity and Stimulus-responsive Fluorescent for Determination of Glyphosate.

Establishing a fast and simple method for determining glyphosate (Glyp) is crucial for safeguarding the environment and protecting human well-being. In this work, a copper benzenedicarboxylate (CuBDC) metal-organic frameworks (MOFs) with peroxidase-like property and stimulus-responsive fluorescent was prepared by binding Cu2+ with terephthalic acid (TA). The presence of Glyp can coordination with Cu2+ ion and block the peroxidase-like properties of CuBDC, thereby suppressing the catalysis the oxidation of TA into fluorescent product 2-hydroxyterephthalic acid (HTA). Based on these facts, a simple, rapid and sensitive fluorescence detection strategy for Glyp was developed. The fluorescence decreases linearly in the 0.5-10µg/mL Glyp concentration range, and the limit of detection was calculated to be 23.99 ng/mL. Furthermore, the dual-functional CuMOFs-based label-free strategy was effectively employed for detecting Glyp in river water samples. With good performance and practicability, this strategy provides a potential application in the convenient and reliable determination of Glyp in the environment.

Advances in the application of defect-engineered metal–organic frameworks as adsorbents during the decontamination of wastewater

Advances in the application of defect-engineered metal–organic frameworks as adsorbents during the decontamination of wastewater

Host-Guest Interactions of Metal-Organic Framework Enable Highly Conductive Quasi-Solid-State Electrolytes for Li-CO2 Batteries.

High-energy lithium (Li)-based batteries, especially rechargeable Li-CO2 batteries with CO2 fixation capability and high energy density, are desirable for electrified transportation and other applications. However, the challenges of poor stability, low energy efficiency, and leakage of liquid electrolytes hinder the development of Li-CO2 batteries. Herein, a highly conductive and stable metal-organic framework-encapsulated ionic liquid (IL@MOF) electrolyte system is developed for quasi-solid-state Li-CO2 batteries. Benefiting from the host-guest interaction of MOFs with open micromesopores and internal IL, the optimized IL@MOF electrolytes exhibit a high ionic conductivity of 1.03 mS cm-1 and a high transference number of 0.80 at room temperature. The IL@MOF electrolytes also feature a wide electrochemical stability window (4.71 V versus Li+/Li) and a wide working temperature (-60 °C ∼ 150 °C). The IL@MOF electrolytes also enable Li+ and electrons transport in the carbon nanotubes-IL@MOF (CNT-IL@MOF) solid cathodes in quasi-solid-state Li-CO2 batteries, delivering a high specific capacity of 13,978 mAh g-1 (50 mA g-1), a long cycle life of 441 cycles (500 mA g-1 and 1000 mAh g-1), and a wide operation temperature of -60 to 150 °C. The proposed MOF-encapsulated IL electrolyte system presents a powerful strategy for developing high-energy and highly safe quasi-solid-state batteries.

Engineering Corrole and Porphyrin-Based Multivariate Metal-Organic Frameworks for Si-H Bond Insertion.

As a contracted porphyrin analogue, corrole shows a more acidic and trinegative/triprotic nature compared with porphyrin in the field of coordination chemistry. However, the direct introduction of corrole into a metal-organic framework is quite difficult due to its lower C2V symmetry. Herein, we report the one-pot synthesis of a series of corrole and porphyrin-based multivariate porphyrinic metal-organic frameworks M1(TCPC)@M2-PCN-222 (M1 = CuIII, MnIII, FeIVCl; TCPC = 5,10,15-tris(4-carboxyphenyl) corrole; M2 = CoII, CuII, NiII, FeIIICl) and applied them to the insertion of a Si-H bond with α-diazoacetates. The resultant FeCl(TCPC)@Ni-PCN-222 displayed the highest efficiency with a turnover number of 796 based on the amount of Fe, which could be reused at least 5 times without a negligible loss of activity. Mechanistic studies disclosed that the reactivity of FeCl(TCPC)@Ni-PCN-222 came from the synergistic effect between FeCl(TCPC) and Ni-PCN-222, in which FeCl(TCPC) acted as the active site in the formation of metal-carbene, whereas Ni-PCN-222 helped condense the silane molecules for boosting the insertion of the Si-H bond.

Upconverting Luminescent MOF for Highly Sensitive Dual-Mode Recognition of Synthetic Dyes.

Lanthanide-based luminescent materials hold promise in sensing applications due to their distinct optical properties. Though advancements in lanthanide-based metal-organic frameworks (MOFs) have enhanced downshifting luminescence, achieving upconversion remains challenging. In this effort, we prepared upconverting ytterbium-doped europium MOFs (x%Yb3+-EuMOFs; x = 10, 20, and 30) via the solvothermal method using 2,6-naphthalenedicarboxylic acid (NDC) as an organic linker. Upconversion (UC) luminescence studies revealed that 30%Yb3+-EuMOF (MOF-3) rapidly detects malachite green (MG, a textile dye) and brilliant green (BG, a food colorant) with excellent sensitivity (λex = 980 nm). Notably, UC luminescence offers a lower detection limit (MG: 36.33 nM, BG: 287.9 nM) compared to the downconverting sensing approach (λex 270 nm), while the related dual-mode luminescence minimizes the risk of false positives from interfering ultraviolet-visible (UV-vis) light-absorbing substances. Upconversion quenching has been linked to the FRET process, with its luminescence assay accurately detecting MG in fish, water, and soil samples under 980 nm excitation (98-105% recovery).

1D Magnetic Nickel‐Carbon Matrix Nanotube Composites Derived from Hydrogen‐Bonded Organic Frameworks and Metal–Organic Frameworks for Electromagnetic Wave Absorption

AbstractHydrogen‐bonded organic frameworks (HOFs) and metal–organic frameworks (MOFs) emerge as promising materials for electromagnetic wave (EMW) absorption, due to their high specific surface area and readily modifiable characteristics. In this study, 1D magnetic nickel‐carbon matrix nanotube composites (Ni‐HMCNTs) from a mixture of HOFs and MOFs (Ni‐HMNTs) for EMW absorption are synthesized. The Ni‐HMNTs are achieved via a one‐step method involving a single‐pot solvothermal reaction among melamine, trimeric acid, and nickel nitrate. This process involves a HOF‐to‐MOF transformation, characterized by the penetration of Ni ions into the HOF structure via a competitive coordination reaction, resulting in the hollow structure of Ni‐HMNTs. Subsequent calcination of Ni‐HMNTs yields Ni‐HMCNTs optimized for EMW absorption. Remarkably, with a filling degree of only 10 wt%, 1.2 Ni‐HMCNTs‐700 (heat‐treated at 700 °C) exhibits exceptional EMW absorption properties, with a minimum reflection loss (RLmin) value of −50.4 dB and a maximum effective absorption bandwidth (EAB) of 7.32 GHz (10.64–17.96 GHz). These findings pave the way for further exploration of magnetically modified HOFs/MOFs for EMW applications.

Nanolabels Prepared by the Entrapment or Self-Assembly of Signaling Molecules for Colorimetric and Fluorescent Immunoassays

Nanomaterials have attracted significant attention as signal reporters for immunoassays. They can directly generate detectable signals or release a large number of signaling elements for readout. Among various nanolabels, nanomaterials composed of multiple signaling molecules have shown great potential in immunoassays. Generally, signaling molecules can be entrapped in nanocontainers or self-assemble into nanostructures for signal amplification. In this review, we summarize the advances of signaling molecules-entrapped or assembled nanomaterials for colorimetric and fluorescence immunoassays. The nanocontainers cover liposomes, polymers, mesoporous silica, metal–organic frameworks (MOFs), various nanosheets, nanoflowers or nanocages, etc. Signaling molecules mainly refer to visible and/or fluorescent organic dyes. The design and application of immunoassays are emphasized from the perspective of nanocontainers, analytes, and analytical performances. In addition, the future challenges and research trends for the preparation of signaling molecules-entrapped or assembled nanolabels are briefly discussed.

Controlled Zn(II) to Co(II) Transmetalation in a Metal–Organic Framework Inducing Single-Ion Magnet Behavior

The intrinsic characteristic features of metal–organic frameworks offer unique, great opportunities to develop novel materials with applications in very diverse fields. Aiming to take advantage of these, the application of post-synthetic methodologies has revealed itself to be a powerful approach to the isolation and structuration of metal ions, molecules, or more complex species, either within MOF channels or reticulated at their network, rendering novel and exciting MOFs with new or improved functionalities. Herein, we report the partial post-synthetic metal exchange of Zn(II) metal ions by Co(II) ones in water-stable three-dimensional CaZn6-MOF 1, derived from the amino acid S-methyl-L-cysteine, allowing us to obtain two novel MOFs with increasing contents of the Co(II) ions Co4%@1 and Co8%@1. Remarkably, the presented post-synthetic metal exchange methodology has two relevant implications for us: (i) it allowed us to obtain two novel MOFs, which were not accessible by direct synthesis, and (ii) enabled us to transform physical properties within this family of isoreticular MOFs from the diamagnetic pristine MOF 1 to MOFs Co4%@1 and Co8%@1, exhibiting field-induced, frequency-dependent, alternating current magnetic susceptibility signals, which are characteristic features of single-molecule magnets.

Diversified applications and synthesis of hydroxamic acids

Owing to the ability to form coordination complexes with several metal ions, hydroxamic acids have been widely used in the fields of medicinal chemistry, mineral flotation, metal–organic frameworks (MOFs), remediation of metal contamination and more. Since three hydroxamic acid-based histone deacetylase (HDAC) inhibitors were approved by the US Food and Drug Administration (FDA) for the treatment of haematologic malignancies, such functional groups have acquired even more attention in synthetic medicinal chemistry. However, application of hydroxamic acids for ore beneficiation is a unique area and has attracted the attention of few researchers. In order to provide insights for chemists in drug development, chelating mineral collector selection, remediation of metal pollution and preparation of MOFs, we summarize the applications of hydroxamic acids in the above-mentioned fields, and then introduce some related synthesis strategies including microwave synthesis, use of continuous flow reactors, solid-phase synthesis and enzymatic synthesis as supplements to classical synthetic methods.

Upconversion Nanoparticle-Anchored Metal-Organic Framework Nanostructures for Remote-Controlled Cancer Optogenetic Therapy.

Optogenetics, a revolutionary technique utilizing light-sensitive proteins to control cellular functions with high spatiotemporal precision, presents a promising avenue for disease treatment; however, its application in cancer therapy remains constrained by limited research. Herein, we introduce a pioneering strategy for remote-controlled optogenetic cancer therapy, synergistically merging optogenetics with ion therapy, which incorporates ion self-supply, in situ ion channel construction, and near-infrared (NIR) light-activated ion therapy, facilitating remote and noninvasive manipulation of cellular activities in deep tissues and living animals. We report the facile synthesis of water-dispersible upconversion nanoparticle (UCNP)-metal-organic framework (MOF) nanohybrids capable of effectively delivering plasmid DNA to cancer cells, thereby enabling the in situ expression of photoactivatable cation channels. The pH-responsive MOF components serve as a reservoir for metal cations, which are released in the acidic microenvironment of tumors, while the UCNP components function as remote-controlled transducers, converting near-infrared (NIR) light into visible light to activate the cation channels and allowing the cancer influx of released metal cations for ion therapy. The proposed remote-controlled cancer optogenetic therapy demonstrates its effectiveness across multiple tumor models, including subcutaneous colon tumors, subcutaneous breast tumors, and orthotopic breast tumors. This study represents a significant step toward the realization of optogenetics in clinics, with substantial potential for advancing cancer therapy.

Boosting the Sustained Release Performance of Metronidazole and Ornidazole with MIL-53(Fe) Derived Spherical Porous Carbon.

Metal-organic framework (MOF) derived spherical porous carbon (SPC) has potential application value in the field of adsorption and sustained release of nitroimidazole drugs. This work used MIL-53(Fe) as a precursor and prepared spherical 3-aminophenol-formaldehyde resin containing MIL-53(Fe) crystals using the advanced Stöber method, followed by the successful preparation of MIL-53(Fe) derived SPC (MSPC) with a structure containing both micropores and mesopores through high-temperature carbonization. The effects of the doping amount of MIL-53(Fe) on the sphericity and particle size of MSPC were investigated. The drug uptake capacity and sustained release performances of MSPC for metronidazole (MNZ) and ornidazole (ONZ) were assessed through batch tests, along with an investigation into the impact of varying pH levels on the sustained release performances. The experimental findings revealed that the drug loading of MNZ and ONZ onto MSPC achieved 111 and 120 mg/g, respectively, with a sustained release time of up to 24 h. The drug loading process adhered to the Langmuir isotherm adsorption model and conformed to the pseudo-second-order kinetics model, whereas the sustained release mechanism was consistent with the Korsmeyer-Peppas model. Furthermore, cytotoxicity and cyclic drug loading experiments indicated that MSPC exhibited good biocompatibility and stability. Therefore, this study provides new ideas for the development of SPC drug carriers.

Size-dependent guest-memory switching of the flexible and robust adsorption characteristics of layered metal-organic frameworks.

Flexible-robust metal-organic frameworks (MOFs), which exhibit unique hybrid nature comprising both flexible and rigid framework characteristics, exhibit high potential for hydrocarbon separations. However, no clear guidelines have been established to regulate their hybrid characteristics owing to limited understanding of their adsorption mechanism. This study investigates the effects of the particle size of a flexible-robust MOF on its adsorption and structural transition behaviors. The robust nature originates from the structural transition of a metastable guest-free structure, while its flexible nature arises from another guest-free structure. The type of guest-free structure is predominantly determined by the particle size; particles below the critical size are trapped in the metastable guest-free structure. Notably, the critical size varies with the type of guest molecule to be removed; consequently, the difference in critical size results in guest-memory characteristics, enabling guest-free structure switching. These results underscore the importance of controlling the particle size to fine-tune hybrid adsorption characteristics of flexible-robust MOFs.

A Multifunctional Tb(III)-Based Metal-Organic Framework for Chemical Conversion of CO2, Fluorescence Sensing of Trace Water and Metamitron.

The utilization of metal-organic frameworks (MOFs) as fluorescent sensors for the detection of environmental and chemical reagent pollutants as well as heterogeneous catalysis for CO2 conversion represents a crucial avenue of research with significant implications for the protection of human health. In this work, a Tb(III)-based three-dimensional metal-organic framework, [Tb(L)·4DMF]n (Tb-MOF) (H3L = 5'-(4-carboxy-3-hydroxyphenyl)-3,3″-dihydroxy-[1,1':3',1″-terphenyl]-4,4″-dicarboxylic acid), has been structurally conformed by single-crystal X-ray crystallography. It possesses a 1D rhombus channel along the [010] direction, featuring a pore size of 6.02 × 9.13 Å. Tb-MOF was proved to be a multifunctional material for a fluorescent sensor and CO2 cycloaddition heterogeneous catalyst material. Fluorescence sensing studies revealed that Tb-MOF demonstrates high sensitivity, selectivity, and favorable regeneration properties, making it an effective chemosensor for detecting the metamitron (MMT) pesticide and trace water in organic solvents. The mechanism of fluorescence quenching by MMT and water was elucidated by a combination of XRD, UV-vis absorption spectra, IR spectra, theoretical calculations, and fluorescence lifetimes. The material was also utilized for the sensing of MMT and water in paper strips. Additionally, the open Tb3+ site as Lewis acidic centers makes Tb-MOF achieve efficiently catalytic conversion for CO2 and epoxides to cyclic carbonates. Moreover, a possible catalytic mechanism for the conversion of carbon dioxide to cyclic carbonates was proposed by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments. It also exhibited recyclability for up to five cycles without noticing an appreciable loss in sensing or catalytic efficiency.