Biphasic interface templated synthesis of wrinkled MOFs for the construction of cascade sensing platform based on the encapsulated gold nanoclusters and enzymes.

The design and construction of MOFs with flower-like structure could afford sufficient space for the immobilization of guests with large size and interconnected transport channels for their mass diffusion although it remains a challenge. Herein, wrinkled Ce-based hierarchically porous UiO-66 (Ce-WUiO-66) with good crystallinity was successfully synthesized for the first time using bicontinuous emulsion composed of 1-heptanol, water and F127 (PEOPPOPEO) surfactant as a template. F127 played a key role in the formation of emulsions as a stabilizer, and meanwhile its PEO segments interacted with MOF precursors to guide the evolvement of crystallized pore walls.

Coordination-Driven Templated Synthesis of Hierarchically Porous Zeolitic Imidazolate Frameworks for Cascade Enzyme Cycle Amplification Coupled Immunoassay.

Although hierarchically porous zeolitic imidazolate frameworks (HPZIFs) not only inherit the intrinsic architectural and chemical stabilities of their microporous counterparts but also afford open space for the efficient mass diffusion of the macromolecules involved, their rational design and construction are still challenging. Herein, HPZIFs with tailorable pore sizes ranging from 18 to 54 nm were successfully fabricated by using a newly developed soft-template-directed strategy. Our success rooted in the fact that the screened PS-PVP-PEO triblock copolymer could effectively coordinate with the metal precursor for the directed crystallization of ZIFs along surfactant assemblies.

Mesoporous MOFs with ROS scavenging capacity for the alleviation of inflammation through inhibiting stimulator of interferon genes to promote diabetic wound healing.

Excessive production of reactive oxygen species (ROS) and inflammation are the key problems that impede diabetic wound healing. In particular, dressings with ROS scavenging capacity play a crucial role in the process of chronic wound healing. Herein, Zr-based large-pore mesoporous metal-organic frameworks (mesoMOFs) were successfully developed for the construction of spatially organized cascade bioreactors.

Hofmeister Effect Promoted the Introduction of Tunable Large Mesopores in MOFs at Low Temperature for Femtomolar ALP Detection.

In addressing the demand for hierarchically mesoporous metal-organic frameworks (HMMOFs) with adjustable large mesopores, a method based on the synergistic effects of low-temperature microemulsions and Hofmeister ions is developed. Low temperature dramatically enhanced the solubility of hydrophobic solvent in the microemulsion core, enlarging the mesopores in HMMOFs replica. Meanwhile, Hofmeister salt-in ions continuously controlled mesopore expansion by modulating the permeability of swelling agent into the microemulsion core.

Photodynamic and Its Concomitant Ion-Interference Synergistic Therapies Based on Functional Hierarchically Mesoporous MOFs.

Although ion-interference therapy (IIT) has become an intriguing option for cancer treatment, the generation of interference ions on-demand remains a challenge. Herein, a nanoplatform based on hierarchically mesoporous metal-organic frameworks (HMMOFs) is adopted to integrate black phosphorus quantum dots (BPQDs) and meso-tetra(4-carboxyphenyl) porphine (TCPP) to realize controllable phosphate anions (PAs) production in a specific cancerous region for IIT. The uniform large mesopores of HMMOFs could guarantee the selective screening and immobilization of ultra-small and monodispersed BPQDs.

Hierarchical large-pore MOFs templated from poly(ethylene oxide)--polystyrene diblock copolymer with tuneable pore sizes.

Diblock copolymer poly(ethylene oxide)--poly(styrene) (PEO--PS) was adopted to template the synthesis of hierarchically porous Ce-based metal-organic frameworks (MOFs) for the first time. By extending the synergistic effect of Hofmeister ions and soft templates into the water-rich system, UiO-66 type Ce-MOFs with a mesopore size of about 15 nm were achieved. Mesopore size could be further tuned up to approximately 23 nm upon introducing 1,3,5-trimethylbenzene to the micelle core of PEO--PS.

Hierarchically Porous MOFs Synthesized by Soft-Template Strategies.

The past few decades have been witnessing the rapid research boom of metal-organic frameworks (MOFs), which are assembled from metal nodes and multitopic organic linkers. In virtue of their modular assembly mode, they can be tailored according to desired functions to satisfy numerous potential applications. However, most initially reported MOFs were restricted to the microporous regime, limiting their practical applications with bulk molecules involved.

Nanoemulsion-directed growth of MOFs with versatile architectures for the heterogeneous regeneration of coenzymes.

As one of the most appealing strategies for the synthesis of nanomaterials with various architectures, emulsion-directed methods have been rarely used to control the structure of metal-organic frameworks (MOFs). Herein, we report a versatile salt-assisted nanoemulsion-guided assembly to achieve continuous architecture transition of hierarchical Zr-based MOFs. The morphology of nanoemulsion can be facilely regulated by tuning the feed ratio of a dual-surfactant and the introduced amount of compatible hydrophobic compounds, which directs the assembly of MOFs with various architectures such as bowl-like mesoporous particle, dendritic nanospheres, walnut-shaped particles, crumpled nanosheets and nanodisks.

Bimetallic Ordered Large-Pore MesoMOFs for Simultaneous Enrichment and Dephosphorylation of Phosphopeptides.

Despite the fact that bimetallic metal-organic frameworks (MOFs) could afford multiple functionalities by a synergistic effect of individual metallic centers, their intrinsic microporous structure frequently restricts their wide applications with bulky molecules involved. An urgent need is consequently triggered to design bimetallic hierarchical mesoporous MOFs (mesoMOFs). Herein, Zr/Ce mesoMOFs with a uniform pore size of up to 8 nm was successfully synthesized by a copolymer template strategy with the aid of a Hoffmeister ion.

Switchable Ionic Transportation in the Nanochannels of the MOFs Triggered by Light and pH.

The construction of a biomimetic ionic channel is of great significance for the fabrication of smart biodevices or logic circuit. Inspired by the selective permeability of the cell membrane toward bioions, a light-induced and pH-modulated artificial nanochannel is herein prepared by integrating the multistimuli-response molecule of carboxylated spiropyran (SP-COOH) into the frameworks of NU-1000 (Zr-based MOFs defined by Northwestern University). The loading density of the SP-COOH could reach as high as 7 wt % while keeping unchanged crystallinity and high porosity.

Specific Screening of Prostate Cancer Individuals Using an Enzyme-Assisted Substrate Sensing Platform Based on Hierarchical MOFs with Tunable Mesopore Size.

Rapid and specific identification of tumor metabolic markers is of great significance. Herein, a convenient, reliable and specific strategy was proposed to screen prostate cancer (PCa) individuals through indirectly quantifying sarcosine, an early indicator of PCa, in the clinical urine samples. The success roots in the rational design of a cascade response model, which takes integrated sarcosine oxidase (SOX) as a specific recognition unit and oxygen-sensitive molecule as a signal reporter.

In Situ Coupling of Catalytic Centers into Artificial Substrate Mesochannels as Super-Active Metalloenzyme Mimics.

Highly evolved substrate channels in natural enzymes facilitate the rapid capture of substrates and direct transfer of intermediates between cascaded catalytic units, thus rationalizing their efficient catalysis. In this study, a nanoscale ordered mesoporous Ce-based metal-organic framework (OMUiO-66(Ce)) is designed as an artificial substrate channel, where MnO is coupled to Ce-O clusters as a super-active catalase (CAT). An in situ soft template reduction strategy is developed to deposit well-dispersed and exposed MnO in the mesochannels of OMUiO-66(Ce).

Zr-MOFs Integrated with a Guest Capturer and a Photosensitizer for the Simultaneous Adsorption and Degradation of 4-Chlorophenol.

A bifunctional metal-organic framework (MOF) was successfully designed to realize the purification of 4-chlorophenol (4-CP) under simulated sunlight irradiation. Owing to the large-size mesopores of the MOF matrix NU-1000, β-CMCD (carboxylic β-cyclodextrin) could be incorporated into the frameworks with a density of 2.4% to pre-enrich the pollutant of 4-CP.

One-pot synthesis of sulfonic acid functionalized Zr-MOFs for rapid and specific removal of radioactive Ba.

Efficient decontamination of radioactive Ba2+ is of great significance to human health and environmental safety. Herein, an adsorbent based on the sulfonic acid functionalized Zr-MOF has been successfully developed, which could efficiently decontaminate radioactive Ba2+ with excellent selectivity, recyclability, a high adsorption capacity up to 60.8 mg g-1 as well as a short adsorption kinetic time of less than 5 min.

Intrinsic Apyrase-Like Activity of Cerium-Based Metal-Organic Frameworks (MOFs): Dephosphorylation of Adenosine Tri- and Diphosphate.

Apyrase is an important family of extracellular enzymes that catalyse the hydrolysis of high-energy phosphate bonds (HEPBs) in ATP and ADP, thereby modulating many physiological processes and driving life activities. Herein, we report an unexpected discovery that cerium-based metal-organic frameworks (Ce-MOFs) of UiO-66(Ce) have intrinsic apyrase-like activity for ATP/ADP-related physiological processes. The abundant Ce /Ce couple sites of Ce-MOFs endow them with the ability to selectively catalyse the hydrolysis of HEPBs of ATP and ADP under physiological conditions.

Efficient enzyme-activated therapy based on the different locations of protein and prodrug in nanoMOFs.

Enzyme-activated prodrug therapy (EAPT) is an effective cancer treatment strategy able to transport non-toxic prodrugs and subsequently convert them into drugs at specific times and locations. However, due to the limitation of easy biodegradability and the membrane-impermeable characteristic of exogenous enzymes, there is a need to exploit suitable carriers for the effective protection and simultaneous delivery of activating enzymes into cancer cells. Herein, hierarchically porous MOFs were employed for the loading of enzyme and prodrug in a single nanocarrier thanks to their different cavity sizes.

Multivalued Logic Assay of the Disease Marker of α-Ketoglutaric Acid by a Luminescent MOF-Based Biosensor.

α-Ketoglutaric acid (α-KA) is an important endogenous metabolite in the Krebs cycle and considered a critical marker for various diseases. Several approaches for identifying α-KA have been reported. However, most of them are limited to single-signal transduction modes in one assay and working in the suspension state, which easily cause quantification errors and lead to false-positive detection results.

One-step coating of commercial Ni nanoparticles with a Ni, N-co-doped carbon shell towards efficient electrocatalysts for CO reduction.

Commercial nickel nanoparticles (Ni NPs) were directly converted to efficient electrocatalysts for CO reduction by urea-Ni solid powder pyrolysis, in which a Ni, N-co-doped graphite carbon shell wraps the Ni NPs in situ. 98.3% CO selectivity was realized with a current density of -20.

Ordered Large-Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion.

Ordered mesoporous metal-organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large-size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting-in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large-pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins.

Glutathione-responsive nanoscale MOFs for effective intracellular delivery of the anticancer drug 6-mercaptopurine.

A glutathione-triggered drug delivery system (DDS) based on nanoscale metal-organic frameworks (NMOFs) is developed, which features an intracellular redox-responsive release of an anticancer drug. Compared to normal cells, the current NMOF-based DDS has 3-fold higher cytotoxicity to cancer cells, prefiguring its great potential for selective cancer therapy.

Structure Engineering of a Lanthanide-Based Metal-Organic Framework for the Regulation of Dynamic Ranges and Sensitivities for Pheochromocytoma Diagnosis.

Exploring innovative technologies to precisely quantify biomolecules is crucial but remains a great challenge for disease diagnosis. Unfortunately, the humoral concentrations of most biotargets generally vary within rather limited scopes between normal and pathological states, while most literature-reported biosensors can detect large spans of targets concentrations, but are less sensitive to small concentration changes, which consequently make them mostly unsatisfactory or even unreliable in distinguishing positives from negatives. Herein, a novel strategy of precisely quantifying the small concentration changes of a certain biotarget by editing the dynamic ranges and sensitivities of a lanthanide-based metal-organic framework (Eu-ZnMOF) biosensor is reported.

Influences of niobium pentoxide on roughness, hydrophilicity, surface energy and protein absorption, and cellular responses to PEEK based composites for orthopedic applications.

To improve the bio-performances of polyetheretherketone (PEEK) for orthopedic applications, submicro-particles of niobium pentoxide (Nb2O5) were synthesized using a sol-gel method, and PEEK/Nb2O5 composites (PNC) with a Nb2O5 content of 25v% (PNC25) and 50v% (PNC50) were fabricated by utilizing a process of pressing-sintering. The results showed that the Nb2O5 particles were not only dispersed in the composites but also exposed on the surface of the composites, which formed submicro-structural surfaces. In addition, the hydrophilicity, surface energy, surface roughness and absorption of proteins of the composites were improved with increasing Nb2O5 content.

Green separation of rare earth elements by valence-selective crystallization of MOFs.

Herein, a novel valence-selective crystallization (VSC) strategy is developed for the precise separation of Ce element from rare earth (RE) mixtures by selectively crystallizing Ce(iv) into pre-designed metal-organic frameworks (MOFs). The designed VSC strategy features fast separation speed, mild separation conditions, pollution-free operation, high separation efficiency, a wide selection range of ligands and extensibility to other elements.

Metal-Organic Frameworks Bearing Dense Alkyl Thiol for the Efficient Degradation and Concomitant Removal of Toxic Cr(VI).

Highly efficient removal of toxic Cr(VI) from aqueous media remains a crucial concern for ecosystem protection and public health. Herein, we demonstrated a new approach to solve this issue by constructing alkyl thiol-containing Zr-based metal-organic framework (MOF) adsorbents using simple and inexpensive mercaptosuccinic acid (MSA) and -dimercaptosuccinic acid (DMSA) as ligands. These chemically stable MOFs could be prepared in an uncomplicated, green, cost-effective, and scalable way.