Water-Stable Fluorous Metal-Organic Frameworks with Open Metal Sites and Amine Groups for Efficient Urea Electrocatalytic Oxidation.

Urea oxidation reaction (UOR) is one of the promising alternative anodic reactions to water oxidation that has attracted extensive attention in green hydrogen production. The application of specifically designed electrocatalysts capable of declining energy consumption and environmental consequences is one of the major challenges in this field. Therefore, the goal is to achieve a resistant, low-cost, and environmentally friendly electrocatalyst. Herein, a water-stable fluorinated Cu(II) metalorganic framework (MOF) {[Cu2 (L)(H2 O)2 ]·(5DMF)(4H2 O)}n (Cu-FMOF-NH2 ; H4 L = 3,5-bis(2,4-dicarboxylic acid)-4-(trifluoromethyl)aniline) is developed utilizing an angular tetracarboxylic acid ligand that incorporates both trifluoromethyl (-CF3 ) and amine (-NH2 ) groups. The tailored structure of Cu-FMOF-NH2 where linkers are connected by fluoride bridges and surrounded by dicopper nodes reveals a 4,24T1 topology. When employed as electrocatalyst, Cu-FMOF-NH2 requires only 1.31 V versus reversible hydrogen electrode (RHE) to deliver 10 mA cm-2 current density in 1.0 m KOH with 0.33 m urea electrolyte and delivered an even higher current density (50 mA cm-2 ) at 1.47 V versus RHE. This performance is superior to several reported catalysts including commercial RuO2 catalyst with overpotential of 1.52 V versus RHE. This investigation opens new opportunities to develop and utilize pristine MOFs as a potential electrocatalyst for various catalytic reactions.

The synergistic effect of Cu-MOF nanoparticles and immunomodulatory agent on SARS-CoV-2 inhibition.

In this work, HKUST-1 and Cu-BDC nanoparticles were used as delivery systems for the early anti-COVID-19 drug, hydroxychloroquine. The antiviral MOF/drug combinations significantly reduced the infectivity of SARS-CoV-2, which can be attributed to the nanometric size of the carriers, the presence of copper in the MOF nodes, and the semi-controlled release of the drug.

Resculpting carbon dots via electrochemical etching.

Substantial efforts are directed into exploring the structure-properties relationships of photoluminescent Carbon dots (C-dots). This study unravels a resculpting mechanism in C-dots that is triggered by electrochemical etching and proceeds via extensive surface oxidation and carbon-carbon breakage. The process results in the gradual shrinkage of the nanoparticles and can enhance the quantum yield by more than half order of magnitude compared to the untreated analogues.

Hydrothermal Synthesis of ZnO Superstructures with Controlled Morphology via Temperature and pH Optimization.

Zinc oxide, as a widely used material in optics, electronics, and medicine, requires a complete overview of different conditions for facile and easily reproducible syntheses. Two types of optimization of ZnO hydrothermal preparation from zinc acetate and sodium hydroxide solution are presented, which allowed for obtaining miscellaneous morphologies of materials. The first was a temperature-controlled synthesis from 100 to 200 °C, using citric acid as a capping agent. The formation of hexagonal rods at the lowest temperature was evidenced, which agglomerated to flower-like structures at 110 and 120 °C. It was followed by transformation to flake-like roses at 160 °C, up to disordered structures composed of nanosized plates (>180 °C). The transformations were generated through a temperature change, which had an impact on the diffusion effect of hydroxide and citrate complexes. The second optimization was the hydrothermal synthesis free of organic additives and it included only a pH variation from 7.5 to 13.5. It was found that by utilizing a slow-dropping process and varying amounts of NaOH solutions, it is possible to obtain well-formed hexagonal pellets at pH 8.0-8.5. Strongly basic conditions of pH 11.0 and 13.5 impeded superstructure formations, giving small elongated particles of ZnO. All samples were characterized by high phase purity and crystallinity, with a specific surface area of 18-37 m2/g, whereas particle size distribution indicated a predominance of small particles (<1 µm).

Speciation of Oxygen Functional Groups on the Carbon Support Controls the Electrocatalytic Activity of Cobalt Oxide Nanoparticles in the Oxygen Evolution Reaction.

The effective use of the active phase is the main goal of the optimization of supported catalysts. However, carbon supports do not interact strongly with metal oxides, thus, oxidative treatment is often used to enhance the number of anchoring sites for deposited particles. In this study, we set out to investigate whether the oxidation pretreatment of mesoporous carbon allows the depositing of a higher loading and a more dispersed cobalt active phase. We used graphitic ordered mesoporous carbon obtained by a hard-template method as active phase support. To obtain different surface concentrations and speciation of oxygen functional groups, we used a low-temperature oxygen plasma. The main methods used to characterize the studied materials were X-ray photoelectron spectroscopy, transmission electron microscopy, and electrocatalytic tests in the oxygen evolution reaction. We have found that the oxidative pretreatment of mesoporous carbon influences the speciation of the deposited cobalt oxide phase. Moreover, the activity of the electrocatalysts in oxygen evolution is positively correlated with the relative content of the COO-type groups and negatively correlated with the C═O-type groups on the carbon support. Furthermore, the high relative content of COO-type groups on the carbon support is correlated with the presence of well-dispersed Co3O4 nanoparticles. The results obtained indicate that to achieve a better dispersed and thus more catalytically active material, it is more important to control the speciation of the oxygen functional groups rather than to maximize their total concentration.

Synthesis and Characterization of Nanoporous Carbon Carriers for Losartan Potassium Delivery.

Losartan potassium is most commonly used for the treatment of hypertension. In recent years, new applications of this drug have emerged, encouraging the design of novel nanoporous carriers for its adsorption and release. The purpose of this study was to synthesize ordered mesoporous carbon vehicles via a soft-templating method altered with the use of nitrogen precursors and via a hard-templating method followed by chitosan functionalization. As a result, the materials obtained differed in nitrogen content as well as in the number of total surface functional groups. The impact of the modification on the physicochemical properties of carbon carriers and their interaction with losartan potassium during adsorption and release processes was examined. The materials were characterized by various morphologies, specific surface areas (101-1180 m2 g-1), and the amount of acidic/basic oxygen-containing functional groups (1.26-4.27 mmol g-1). These features, along with pore sizes and volumes, had a key effect on the sorption capacity of carbon carriers towards losartan potassium (59-161 mg g-1). Moreover, they contributed to the differential release of the drug (18.56-90.46%). Losartan potassium adsorption onto the surface of carbonaceous materials was mainly based on the formation of hydrogen bonds and π-π interactions and followed the Langmuir type isotherm. It has been shown that the choice of the method of carbon carriers' synthesis and their modification allows for the precise control of the kinetics of the losartan potassium release from their surface, resulting in rapid or sustained drug liberation.

The Current Status of MOF and COF Applications.

The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real-world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications.

Amine-Grafted Mesoporous Carbons as Benzocaine-Delivery Platforms.

Smart porous carriers with defined structure and physicochemical properties are required for releasing the therapeutic drug with precise control of delivery time and location in the body. Due to their non-toxicity, ordered structure, and chemical and thermal stability, mesoporous carbons can be considered modern carriers for active pharmaceutical ingredients whose effectiveness needs frequent dosing algorithms. Here, the novel benzocaine delivery systems based on ordered mesoporous carbons of the cubic structure were obtained with the use of a hard template method and functionalization with amine groups at 40 °C for 8 h. It has been shown that amine grafting strongly modifies the surface chemistry and textural parameters of carbons. All samples indicated good sorption ability towards benzocaine, with evident improvement following the functionalization with the amine groups. The sorption capacity and drug release kinetics were strongly affected by the porosity of carbon carriers and the surface functional groups. The smallest amount of benzocaine (~12%) was released from pristine mesoporous carbon, which could be correlated with strong API-carrier interactions. Faster and more efficient release of the drug was observed in the case of triethylenetetramine modified carbon (~62%). All benzocaine delivery platforms based on amine-grafted mesoporous carbons revealed high permeability through the artificial membrane.

Overcoming the paracetamol dose challenge with wrinkled mesoporous carbon spheres.

Paracetamol is the most commonly used antipyretic and analgesic drug in the world. The key challenge in paracetamol therapy is associated with the frequency of the dosing. Depending on the gastric filling within 10-20 min paracetamol is released and rapidly absorbed from the gastrointestinal tract. Therefore, it must be taken three or four times a day. To address the dose challenge it is desirable that the paracetamol release profile follows the zero-order kinetic model (constant rate of drug release per unit time). This goal can be achieved by using a suitable porous carrier system. Herein, non-toxic wrinkled mesoporous carbons with unique morphology were synthesized via the hard template method as new carriers for paracetamol. These particles can precisely modulate the release of paracetamol over 24 h in a simulated gastric fluid according to the zero-order kinetic model completely eliminating the initial burst release. Overall, these systems could significantly enhance the bioavailability of paracetamol and prolong its therapeutic effect in numerous diseases such as cold, flu, COVID-19, and severe pain.

Design of Paracetamol Delivery Systems Based on Functionalized Ordered Mesoporous Carbons.

The oxidized ordered mesoporous carbons of cubic and hexagonal structure obtained by two templating methods (soft and hard) were applied for the first time as delivery systems for paracetamol-the most common antipyretic and analgesic drug in the world. The process of carbon oxidation was performed using an acidic ammonium persulfate solution at 60 °C for 6 h. The functionalization was found to reduce the specific surface area and pore volume of carbon materials, but it also led to an increasing number of acidic oxygen-containing functional groups. The most important element and the novelty of the presented study was the evaluation of adsorption and release ability of carbon carriers towards paracetamol. It was revealed that the sorption capacity and the drug release rate were mainly affected by the materials' textural parameters and the total amount of surface functional groups, notably different in pristine and oxidized samples. The adsorption of paracetamol on the surface of ordered mesoporous carbons occurred according to different mechanisms: donor-acceptor complexes and hydrogen bond formation. The adsorption kinetics was assessed using pseudo-first- and pseudo-second-order models. The regression results indicated that the adsorption kinetics was more accurately represented by the pseudo-second-order model. Paracetamol was adsorbed onto the carbon materials studied following the Langmuir type isotherm. The presence of oxygen-containing functional groups on the surface of ordered mesoporous carbons enhanced the amount of paracetamol adsorbed and its release rate. The optimal drug loading capacity and expected release pattern exhibited oxidized ordered mesoporous carbon with a hexagonal structure obtained by the hard template method.

Controlling the morphology of metal-organic frameworks and porous carbon materials: metal oxides as primary architecture-directing agents.

Owing to their large ratio of surface area to mass and volume, metal-organic frameworks and porous carbons have revolutionized many applications that rely on chemical and physical interactions at surfaces. However, a major challenge today is to shape these porous materials to translate their enhanced performance from the laboratory into macroscopic real-world applications. In this review, we give a comprehensive overview of how the precise morphology control of metal oxides can be transferred to metal-organic frameworks and porous carbon materials. As such, tailored material structures can be designed in 0D, 1D, 2D, and 3D with considerable implications for applications such as in energy storage, catalysis and nanomedicine. Therefore, we predict that major research advances in morphology control of metal-organic frameworks and porous carbons will facilitate the use of these materials in addressing major needs of the society, especially the grand challenges of energy, health, and environment.