[Preparation of two tanshinone â ¡_A-astragaloside â £ co-loaded nano-delivery systems and in vitro antitumor activity comparison].

This study screened excellent carriers for co-loading tanshinone Ⅱ_A(TSA) and astragaloside Ⅳ(As) to construct antitumor nano-drug delivery systems for TSA and As. TSA-As microemulsions(TSA-As-MEs) were prepared by water titration. TSA-As metal-organic framework(MOF) nano-delivery system was prepared by loading TSA and As in MOF by the hydrothermal method. Dynamic light scattering(DLS), transmission electron microscopy(TEM), and scanning electron microscopy(SEM) were used to characterize the physicochemical properties of the two preparations. Drug loading was determined by HPLC and the effects of the two preparations on the proliferation of vascular endothelial cells, T lymphocytes, and hepatocellular carcinoma cells were detected by the CCK-8 method. The results showed that the particle size, Zeta potential, and drug loading of TSA-As-MEs were(47.69±0.71) nm,(-14.70±0.49) mV, and(0.22±0.01)%, while those of TSA-As-MOF were(258.3±25.2) nm,(-42.30 ± 1.27) mV, and 15.35%±0.01%. TSA-As-MOF was superior to TSA-As-MEs in drug loading, which could inhibit the proliferation of bEnd.3 cells at a lower concentration and improve the proliferation ability of CTLL-2 cells significantly. Therefore, MOF was preferred as an excellent carrier for TSA and As co-loading.

Nickel-Based Metal-Organic Frameworks as Electrocatalysts for the Oxygen Evolution Reaction (OER).

The exploration of earth-abundant electrocatalysts with high performance for the oxygen evolution reaction (OER) is eminently desirable and remains a significant challenge. The composite of the metal-organic framework (MOF) Ni10Co-BTC (BTC = 1,3,5-benzenetricarboxylate) and the highly conductive carbon material ketjenblack (KB) could be easily obtained from the MOF synthesis in the presence of KB in a one-step solvothermal reaction. The composite and the pristine MOF perform better than commercially available Ni/NiO nanoparticles under the same conditions for the OER. Activation of the nickel-cobalt clusters from the MOF can be seen under the applied anodic potential, which steadily boosts the OER performance. Ni10Co-BTC and Ni10Co-BTC/KB are used as sacrificial agents and undergo structural changes during electrochemical measurements, the stabilized materials show good OER performances.

Synthesis of a Chiral 3,6T22-Zn-MOF with a T-Shaped Bifunctional Pyrazole-Isophthalate Ligand Following the Principles of the Supramolecular Building Layer Approach.

The metal-organic framework (MOF) [Zn(Isa-az-tmpz)]·~1-1.5 DMF with the novel T-shaped bifunctional linker 5-(2-(1,3,5-trimethyl-1H-pyrazol-4-yl)azo)isophthalate (Isa-az-tmpz) was obtained as a conglomerate of crystals with varying degrees of enantiomeric excess in the chiral tetragonal space groups P43212 or P41212. A topological analysis of the compound resulted in the rare 3,6T22-topology, deviating from the expected rtl-topology, which has been found before in pyrazolate-isophthalate-functionalized MOFs using the supramolecular building layer (SBL) approach. 3,6T22-[Zn(Isa-az-tmpz)]·~1-1.5 DMF is a potentially porous, three-dimensional structure with DMF molecules included in the corrugated channels along the a and b-axis of the as synthesized material. The small trigonal cross-section of about 6 × 4 Å (considering the van der Waals surface) prevents the access of N2 and Ar under cryogenic conditions. After activation, only smaller H2 (at 87 K) and CO2 (at 195 K) are allowed for gas uptakes of 2 mmol g-1 and 5.4 mmol g-1, respectively, in the ultramicroporous material, for which a BET surface area of 496 m2·g-1 was calculated from CO2 adsorption. Thermogravimetric analysis of the compound shows a thermal stability of up to 400 °C.

Metal-Organic Frameworks as Catalyst Supports: Influence of Lattice Disorder on Metal Nanoparticle Formation.

Because of their high tunability and surface area, metal-organic frameworks (MOFs) show great promise as supports for metal nanoparticles. Depending on the synthesis route, MOFs may contain defects. Here, we show that highly crystalline MIL-100(Fe) and disordered Basolite® F300, with identical iron 1,3,5-benzenetricarboxylate composition, exhibit very divergent properties when used as a support for Pd nanoparticle deposition. While MIL-100(Fe) shows a regular MTN-zeotype crystal structure with two types of cages, Basolite® F300 lacks long-range order beyond 8 Šand has a single-pore system. The medium-range configurational linker-node disorder in Basolite® F300 results in a reduced number of Lewis acid sites, yielding more hydrophobic surface properties compared to hydrophilic MIL-100(Fe). The hydrophilic/hydrophobic nature of MIL-100(Fe) and Basolite® F300 impacts the amount of Pd and particle size distribution of Pd nanoparticles deposited during colloidal synthesis and dry impregnation methods, respectively. It is suggested that polar (apolar) solvents/precursors attractively interact with hydrophilic (hydrophobic) MOF surfaces, allowing tools at hand to increase the level of control over, for example, the nanoparticle size distribution.

Improving bioelectrochemical performance by sulfur-doped titanium dioxide cooperated with Zirconium based metal-organic framework (S-TiO2@MOF-808) as cathode in microbial fuel cells.

The sulfur-doped titanium dioxide (S-TiO2) cooperated with Zirconium based on a kind of metal-organic framework (MOF-808) was successfully prepared as cathode catalyst (S-TiO2@MOF-808) of microbial fuel cell (MFC) by two-step hydrothermal reaction. The particle size was approximately 5 µm, and the spherical S-TiO2 particle was attached to the surface of MOF-808 as irregular block solid. Zr-O, C-O and O-H bond were indicated to exist in S-TiO2@MOF-808. When n (Zr4+): n(Ti4+) was 1: 5, S-TiO2@MOF-808 showed better oxygen reduction reaction (ORR). The introduction of S-TiO2 restrained the framework collapse of MOF-808, S-TiO2@MOF-808 showed much higher catalytic stability in reaction. The recombination of sulfur and TiO2 reduced the charge transfer resistance, accelerated the electron transfer rate, and improved ORR greatly. The maximum power density of S-TiO2@MOF-808-MFC was 84.05 mW/m2, about 2.17 times of S-TiO2-MFC (38.64 mW/m2). The maximum voltage of S-TiO2@MOF-808-MFC was 205 mV, and the stability was maintained for 6 d.

The Challenge of Water Competition in Physical Adsorption of CO2 by Porous Solids for Carbon Capture Applications - A Short Perspective.

With ever-increasing efforts to design sorbent materials to capture carbon dioxide from flue gas and air, this perspective article is provided based on nearly a decade of collaboration across science, engineering, and industry partners. A key point learned is that a holistic view of the carbon capture problem is critical. While researchers can be inclined to value their own fields and associated metrics, often, key parameters are those that enable synergy between materials and processes. While the role of water in the chemisorption of CO2 is well-studied, in this perspective, it is hoped to highlight the often-overlooked but critical role of water in assessing the potential of a physical adsorbent for CO2 capture. This is a challenge that requires interdisciplinarity. As such, this document is written for a general audience rather than experts in any specific discipline.

Effect of Silicone Patch Containing Metal-organic Framework on Hypertrophic Scar Suppression.

BACKGROUND/AIM: Hypertrophic scars (HS) are an abnormal cutaneous condition of wound healing characterized by excessive fibrosis and disrupted collagen deposition. This study assessed the potential of a silicone patch embedded with chemically stable zirconium-based metal-organic frameworks (MOF)-808 structures to mitigate HS formation using a rabbit ear model. MATERIALS AND METHODS: A silicone patch was strategically engineered by incorporating Zr-MOF-808, a composite structure comprising metal ions and organic ligands. Structural integrity of the Zr-MOF-808 silicone patch was validated using scanning electron microscopy and X-ray diffraction analysis. The animals were divided into three groups: a control, no treatment group (Group 1), a silicone patch treatment group (Group 2), and a group treated with a 0.2% loaded Zr-MOF-808 silicone patch (Group 3). HS suppression effects were quantified using scar elevation index (SEI), dorsal skin thickness measurements, and myofibroblast protein expression. RESULTS: Histopathological examination of post-treatment HS samples revealed substantial reductions in SEI (34.6%) and epidermal thickness (49.5%) in Group 3. Scar hyperplasia was significantly diminished by 53.5% (p<0.05), while collagen density declined by 15.7% in Group 3 compared to Group 1. Western blot analysis of protein markers, including TGF-ß1, collagen-1, and α-SMA, exhibited diminished levels by 8.8%, 12%, and 21.3%, respectively, in Group 3, and substantially higher levels by 21.9%, 27%, and 39.9%, respectively, in Group 2. On the 35th day post-wound generation, Zr-MOF-808-treated models exhibited smoother, less conspicuous, and flatter scars. CONCLUSION: Zr-MOF-808-loaded silicone patch reduced HS formation in rabbit ear models by inducing the proliferation and remodeling of the wound healing process.

Site-Specific Antibody Assembly on Nanoparticles via a Versatile Coating Method for Improved Cell Targeting.

Antibody-nanoparticle conjugates are promising candidates for precision medicine. However, developing a controllable method for conjugating antibodies to nanoparticles without compromising the antibody activity represents a critical challenge. Here, a facile and generalizable film-coating method is presented using zeolitic imidazole framework-8 (ZIF-8) to immobilize antibodies on various nanoparticles in a favorable orientation for enhanced cell targeting. Different model and therapeutic antibodies (e.g., Herceptin) are assembled on nanoparticles via a biomineralized film-coating method and exhibited high antibody loading and targeting efficiencies. Importantly, the antibodies selectively bind to ZIF-8 via their Fc regions, which favorably exposes the functional Fab regions to the biological target, thus improving the cell targeting ability of antibody-coated nanoparticles. In combination, molecular dynamics simulations and experimental studies on antibody immobilization, orientation efficiency, and biofunctionality collectively demonstrate that this versatile site-specific antibody conjugation method provides effective control over antibody orientation and leads to improved cell targeting for a variety of nanoparticles.

Combination of deep eutectic solvent and functionalized metal-organic frameworks as a green process for the production of 5-hydroxymethylfurfural and furfural from sugars.

Biomass is an abundant and sustainable resource that can be converted into energy and chemicals. Therefore, the development of efficient methods for the conversion of biomass into platform intermediates is crucial. In this study, the one-pot conversion of sugars into 5-hydroxymethylfurfural (HMF) and furfural was achieved using the metal-organic framework combined with metal ions [MIL-101(Cr)] as a high-activity catalyst, and a deep eutectic solvent (choline chloride and lactic acid) as a green solvent. The optimal temperature, time, amount of catalyst used, and amount of deep eutectic solvent used were all determined. The highest HMF yield of 49.74% and furfural yield of 55.90% were obtained. The recyclability of the catalysts and deep eutectic solvent was also investigated. After three reaction runs, the HMF yield was still nearly 30.00%. Finally, the MIL-101(Cr) catalytic system was selected to study the kinetic mechanism underlying the conversion of glucose into HMF.

MOFGalaxyNet: a social network analysis for predicting guest accessibility in metal-organic frameworks utilizing graph convolutional networks.

Metal-organic frameworks (MOFs), are porous crystalline structures comprising of metal ions or clusters intricately linked with organic entities, displaying topological diversity and effortless chemical flexibility. These characteristics render them apt for multifarious applications such as adsorption, separation, sensing, and catalysis. Predominantly, the distinctive properties and prospective utility of MOFs are discerned post-manufacture or extrapolation from theoretically conceived models. For empirical researchers unfamiliar with hypothetical structure development, the meticulous crystal engineering of a high-performance MOF for a targeted application via a bottom-up approach resembles a gamble. For example, the precise pore limiting diameter (PLD), which determines the guest accessibility of any MOF cannot be easily inferred with mere knowledge of the metal ion and organic ligand. This limitation in bottom-up conceptual understanding of specific properties of the resultant MOF may contribute to the cautious industrial-scale adoption of MOFs.Consequently, in this study, we take a step towards circumventing this limitation by designing a new tool that predicts the guest accessibility-a MOF key performance indicator-of any given MOF from information on only the organic linkers and the metal ions. This new tool relies on clustering different MOFs in a galaxy-like social network, MOFGalaxyNet, combined with a Graphical Convolutional Network (GCN) to predict the guest accessibility of any new entry in the social network. The proposed network and GCN results provide a robust approach for screening MOFs for various host-guest interaction studies.

Nanotechnology-assisted treatment of pharmaceuticals contaminated water.

The presence of pharmaceutical compounds in wastewater due to an increase in industrialization and urbanization is a serious health concern. The demand for diverse types of pharmaceutical compounds is expected to grow as there is continuous improvement in the global human health standards. Discharge of domestic pharmaceutical personal care products and hospital waste has aggravated the burden on wastewater management. Further, the pharmaceutical water is toxic not only to the aquatic organism but also to terrestrial animals coming in contact directly or indirectly. The pharmaceutical wastes can be removed by adsorption and/or degradation approach. Nanoparticles (NPs), such as 2D layers materials, metal-organic frameworks (MOFs), and carbonaceous nanomaterials are proven to be more efficient for adsorption and/or degradation of pharmaceutical waste. In addition, inclusion of NPs to form various composites leads to improvement in the waste treatment efficacy to a greater extent. Overall, carbonaceous nanocomposites have advantage in the form of being produced from renewable resources and the nanocomposite material is biodegradable either completely or to a great extent. A comprehensive literature survey on the recent advancement of pharmaceutical wastewater is the focus of the present article.

Metal-organic frameworks (MOFs) as biomolecules drug delivery systems for anticancer purposes.

Metal-organic frameworks (MOF) have been studied for infinite applications. Among these, anticancer therapy has surely attracted great interest due to the intrinsic characteristics of MOFs: large surface area, tuneable porosity, remarkable biocompatibility, easy production, and the possibility to further functionalize the realized nanoparticles are the main reasons that make MOFs the ideal candidates to overcome traditional chemotherapy limits and resistance. Smart MOFs are becoming particularly relevant, as they can be activated by specific endogenous or exogenous stimuli and release their cargo only under the selected conditions. Tumor microenvironment (TME) offers the possibility to take advantage of its peculiar composition to design and build smart nanoparticles, able to selectively release the therapeutic payload only in the environment surrounding cancer cells or directly in the intracellular environment. In this review, we have summarized novel and innovative works describing anticancer MOF-based nanoparticles loaded with biomolecules published in the last three years. The reported papers have been selected with special focus on TME-responsive MOFs and the synthetic procedures employed by research groups have been reported for almost all works, to further underline the myriad of possibilities offered by these hybrid metal-organic structures.

Gold nanoparticle-glutathione functionalized MOFs as hydrophilic materials for the selective enrichment of glycopeptides.

Herein, a novel zwitterionic hydrophilic metal-organic framework (MOF)-functionalized material was synthesized through grafting l-glutathione (GSH) onto the Au which acts as the intermediate layer to modify the base material (PEI-ZIF-8) by the sulfhydryl group provided by GSH and the affinity provided by Au (denoted as PEI-ZIF-8@Au@GSH). The obtained product was employed to capture glycopeptides. Benefit from its excellent hydrophilic properties, abundant amphoteric ions, and unique large specific surface area, this material demonstrated amazing ability in the enrichment and identification of glycopeptides. As a result, the PEI-ZIF-8@Au@GSH displayed high sensitivity (as low as 2 fmol), excellent binding capacity (500 mg/g), outstanding enrichment selectivity (maximum mass ratio HRP to BSA is 1:1000) toward glycopeptides, and the ability to recycle at least five times. Furthermore, 35 and 51 glycopeptides were successfully detected from 5 µL human saliva and human serum respectively in the examination of the actual sample by MALDI-TOF MS. The above results indicated that the PEI-ZIF-8@Au@GSH had a satisfactory potential in the field of glycoproteomics.

Selective Adsorption of Aqueous Diclofenac Sodium, Naproxen Sodium, and Ibuprofen Using a Stable Fe3O4-FeBTC Metal-Organic Frameworka.

The FeBTC metal-organic framework (MOF) incorporated with magnetite is proposed as a novel material to solve water contamination with last generation pollutants. The material was synthesized by in situ solvothermal methods, and Fe3O4 nanoparticles were added during FeBTC MOF synthesis and used in drug adsorption. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy characterized the materials, with N2-physisorption at 77 K. Pseudo-second-order kinetic and Freundlich models were used to describe the adsorption process. The thermodynamic study revealed that the adsorption of three drugs was a feasible, spontaneous exothermic process. The incorporation of magnetite nanoparticles in the FeBTC increased the adsorption capacity of pristine FeBTC. The Fe3O4-FeBTC material showed a maximum adsorption capacity for diclofenac sodium (DCF), then by ibuprofen (IB), and to a lesser extent by naproxen sodium (NS). Additionally, hybridization of the FeBTC with magnetite nanoparticles reinforced the most vulnerable part of the MOF, increasing the stability of its thermal and aqueous media. The electrostatic interaction, H-bonding, and interactions in the open-metal sites played vital roles in the drug adsorption. The sites' competition in the multicomponent mixture's adsorption showed selective adsorption (DCF) and (NS). This work shows how superficial modification with a low-surface-area MOF can achieve significant adsorption results in water pollutants.

A Review on Metal-Organic Frameworks as Congenial Heterogeneous Catalysts for Potential Organic Transformations.

Metal-organic frameworks (MOFs) have emerged as versatile candidates of interest in heterogeneous catalysis. Recent research and developments with MOFs positively endorse their role as catalysts in generating invaluable organic compounds. To harness the full potential of MOFs in value-added organic transformation, a comprehensive look at how these materials are likely to involve in the catalytic processes is essential. Mainstays of MOFs such as metal nodes, linkers, encapsulation materials, and enveloped structures tend to produce capable catalytic active sites that offer solutions to reduce human efforts in developing new organic reactions. The main advantages of choosing MOFs as reusable catalysts are the flexible and robust skeleton, regular porosity, high pore volume, and accessible synthesis accompanied with cost-effectiveness. As hosts for active metals, sole MOFs, modified MOFs, and MOFs have made remarkable advances as solid catalysts. The extensive exploration of the MOFs possibly led to their fast adoption in fabricating new biological molecules such as pyridines, quinolines, quinazolinones, imines, and their derivatives. This review covers the varied MOFs and their catalytic properties in facilitating the selective formation of the product organic moieties and interprets MOF's property responsible for their elegant performance.

Development of a solid-phase microextraction method for fast analysis of cyclic volatile methylsiloxanes in water.

Cyclic volatile methylsiloxanes (cVMS) are widely used in consumer products and commonly detected in the environment. There are challenges in the analysis of cVMS because of their ubiquitous use which can introduce high background contamination. The current study introduces a sample preparation method based on headspace of solid-phase microextraction (SPME) for monitoring the cVMS in waters. Efforts were made to reduce the background contamination during sample preparation and instrument analysis. A laboratory prepared MIL-101 coating was prepared using polysulfone instead of polydimethylsiloxane as adhesive to avoid the contamination. The extraction performance of the MIL-101 fiber was optimized and evaluated. The optimized extraction time and temperature were 60 min and 40 °C, respectively. The method quantification limits of the MIL-101 fiber for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) in water were 0.15 ng mL-1, 0.14 ng mL-1, and 0.27 ng mL-1, respectively. The extraction efficiency of the proposed MIL-101 fiber was comparable to the commercial polydimethylsiloxane/divinylbenzene fiber. The developed method was applied to analyze the cVMS in wastewater treatment plant and the concentrations in the barscreen and in the aeration tank ranged from 0.73 to 3.3 ng mL-1 and 7.74-85.1 ng mL-1, respectively. The MIL-101 fiber was also applied to study the photodegradation of the cVMS in water under simulated sunlight. Approximately 25%, 20%, and 45% of D4, D5, and D6, respectively, were degraded after 10 h exposure.

Probing the structure, stability and hydrogen adsorption of lithium functionalized isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn) by density functional theory.

Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen.

An Inhalable Theranostic System for Local Tuberculosis Treatment Containing an Isoniazid Loaded Metal Organic Framework Fe-MIL-101-NH2-From Raw MOF to Drug Delivery System.

The theranostic approach to local tuberculosis treatment allows drug delivery and imaging of the lungs for a better control and personalization of antibiotic therapy. Metal-organic framework (MOF) Fe-MIL-101-NH2 nanoparticles were loaded with isoniazid. To optimize their functionality a 23 factorial design of spray-drying with poly(lactide-co-glycolide) and leucine was employed. Powder aerodynamic properties were assessed using a twin stage impinger based on the dose emitted and the fine particle fraction. Magnetic resonance imaging (MRI) contrast capabilities were tested on porous lung tissue phantom and ex vivo rat lungs. Cell viability and uptake studies were conducted on murine macrophages RAW 246.9. The final product showed good aerodynamic properties, modified drug release, easier uptake by macrophages in relation to raw isoniazid-MOF, and MRI contrast capabilities. Starting from raw MOF, a fully functional inhalable theranostic system with a potential application in personalized tuberculosis pulmonary therapy was developed.

Fabrication of Monodisperse Flower-Like Coordination Polymers (CP) Microparticles by Spray Technique.

In this manuscript, we have developed an efficient spraying method to successfully fabricate a series of flower-like coordination polymers (CP) microparticles, including Co/BDC (1,4-benzenedicarboxylate) metal organic frameworks (MOF) and infinite coordination polymers (ICP) microparticles, as well as Ni-Co/BDC MOF and Zn/DOBDC (2,5-dioxido-1,4-benzenedicarboxylate) MOF. The spraying method has shown high efficiency and universality in synthesizing the flower-like CP. The crystalline structure can be adjusted by varying the solvent composition in the spraying process. SEM observation demonstrated the MOF and ICP microparticles possess the similar flower-like structure, which is composed of nanoflakes with smooth surface, and the flower-like microparticles could be monodisperse with as low as 5% polydispersity. Moreover, the fabrication of the flower-like CP microparticles by spraying has a wide operation window, because there is no need to precisely control the experiment conditions, like solvents, concentration, and spray order. Due to the practicality of spray technique, this work would pave the way for the manufacture of the flower-like materials and have great potential in applications of catalysis, sensor, energy storage, and so on.