In-silico green toxicology approach toward discovering safer ligands for development of safe-by-design metal-organic frameworks.

A vast variety of chemical compounds have been fabricated and commercialized, they not only result in industrial exposure during manufacturing and usage, but also have environmental impacts throughout their whole life cycle. Consequently, attempts to assess the risk of chemicals in terms of toxicology have never ceased. In-silico toxicology, also known as predictive toxicology, has advanced significantly over the last decade as a result of the drawbacks of experimental investigations. In this study, ProTox-III was applied to predict the toxicity of the ligands used for metal-organic framework (MOF) design and synthesis. Initially, 35 ligands, that have been frequently utilized for MOF synthesis and fabrication, were selected. Subsequently, canonical simplified molecular-input line-entry system (SMILES) of ligands were extracted from the PUBCHEM database and inserted into the ProTox-III online server. Ultimately, webserver outputs including LD50 and the probability of toxicological endpoints (cytotoxicity, carcinogenicity, mutagenicity, immunotoxicity, and ecotoxicity) were obtained and organized. According to retrieved LD50 data, the safest ligand was 5-hydroxyisophthalic. In contrast, the most hazardous ligand was 5-chlorobenzimidazole, with an LD50 of 8 mg/kg. Among evaluated endpoints, ecotoxicity was the most active and was detected in several imidazolate ligands. This data can open new horizons in design and development of green MOFs.

Unveiling the remarkable simultaneous adsorption-photocatalytic potential of Ag nanoparticles-anchored phosphotungestic acid loaded ZIF-8 for Congo red removal.

This research paper presents a direct approach to synthesize AgNPs deposited on polyoxometalate/ZIF-8 on-site (referred to as AgNPS@PW@ZIF-8) to develop a highly efficient photocatalyst in the water treatment. Phosphotungestic acid (PW) serves a multi-purpose in this context: it acts as a bridge layer between AgNPs and Zeolitic Imidazolate Framework-8 (ZIF-8), a local reducing agent, and a catalyst for electron transfer during the photocatalysis process. A comprehensive characterization of the resulting nanostructure was performed utilizing an array of techniques, such as XRD, FTIR, EDX, TEM, BET, Raman, and TGA. The nanostructure that was created exhibited effective removal of Congo red at different pH levels via a combination of simultaneous adsorption and photocatalysis. After 60 min at pH 7, the dye molecules were completely eliminated in the presence of 0.5 g/L AgNPS@PW@ZIF-8 at room temperature. The charge transfer can be facilitated by the PW bridge layer connecting AgNPs and ZIF-8, owing to the photoactive characteristics and strong electron transfer capabilities of PW molecules. Strong electron transferability of PW between Ag nanoparticles and ZIF-8 facilitates charge transfer and significantly improves the photocatalytic performance of ZIF-8. Moreover, the nanostructure demonstrated great structural stability and recyclability, sustaining a high efficiency of removal throughout five consecutive cycles through the implementation of a simple procedure. Widespread applications of the developed nanostructure in aquatic environments for adsorption and photocatalytic reactions are possible.

Developing a magnetic metal organic framework of copper bearing a mixed azido/butane-1,4-dicarboxylate bridge: magnetic and gas adsorption properties.

A magnetic metal organic framework {[Cu(but-1,4-dc)0.5(N3)(H2O)]·H2O}n (MFUM-1(Cu)) (but-1,4-dc = butane-1,4-dicarboxylate) was synthesized and characterized structurally and magnetically. In MFUM-1(Cu), each CuII ion has a distorted octahedral geometry with an obvious Jahn-Teller distortion, where the coordination environment is composed of mixed EO-azido/aliphatic based carboxylate/H2O threefold bridges. These bridges extend the structure of MFUM-1(Cu) in two dimensions by covalent connectivity and form square-shaped channels. Also, a study was done to determine the effectiveness of sonochemical synthesis for the preparation of nano-sheets of MFUM-1(Cu) and subsequently the influence of particle size on physical properties such as magnetic behavior and thermal stability. The particles were characterized by elemental analyses, infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD) analyses. The effects of parameters such as concentration, solvent, and reaction time on the size distribution, morphology, and yield of product were carefully studied. The magnetic properties of MFUM-1(Cu) and corresponding nano-structure were examined which indicated metamagnetism with strong intrachain ferromagnetic coupling versus the weak interchain antiferromagnetic coupling. Finally, the application of MFUM-1(Cu) in the separation of carbon dioxide from nitrogen and also from methane was theoretically investigated. High calculated selectivity of CO2 over N2 and CH4 reveals the potential application of MFUM-1(Cu) in practical systems of gas separation.

Zeolitic imidazolate framework-8 for efficient adsorption and removal of Cr(VI) ions from aqueous solution.

Heavy metals are emerging toxic pollutants in which the development of advanced materials for their efficient adsorption and separation is thus of great significance in environmental sciences point of view. In this study, one of the zinc-based zeolitic imidazolate framework materials, known as ZIF-8, has been synthesized and used for chromium(VI) contaminant removal from water for the first time. The as-synthesized ZIF-8 adsorbent was characterized with different methodologies such as powder X-ray diffraction (XRD), thermo-gravimetric analysis, FT-IR, nuclear magnetic resonance spectroscopy, and UV-Vis spectra of solid state. Various factors affecting removal percentage (efficiency) are experimentally investigated including pH of solution, adsorbent dosage, contact time and initial concentration of Cr(VI) to achieve the optimal condition. The obtained results indicate that the ZIF-8 shows good performance for the Cr(VI) removal from aqueous solution so that 60 min mixing of 2 g of ZIF-8 adsorbent with the 2.5 ppm of Cr(VI) solution in a neutral environment will result in the highest separation efficiency around 70%. The time needed to reach the equilibrium (maximum separation efficiency) is only 60 min for a concentration of 5 mg L-1. Structure stability in the presence of water is also carefully examined by XRD determination of ZIF-8 under different contact times in aqueous solution, which suggests that the structure is going to be destructed after 60 min immersed in solution. Electrostatic interaction of Cr(VI) anions by positively charged ZIF-8 is responsible for Cr(VI) adsorption and separation. Moreover, equilibrium adsorption study reveals that the Cr(VI) removal process using ZIF-8 nicely fits the Langmuir and Toth isotherm models which mean the adsorbent has low heterogeneous surface with different distributions of adsorption energies during Cr(VI) adsorption. Equilibrium adsorption capacity is observed around 0.25 for 20 mg L-1 of initial Cr(VI) solutions.