Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies.

The crystal structure of the metal-organic framework (MOF), {Mn2(1,4-bdc)2(DMF)2}n (1) (1,4-bdcH2, 1,4-benzenedicarboxylic acid; DMF, N,N-dimethylformamide), is known for a long time; however, its desolvated structure, {Mn2(1,4-bdc)2}n (1'), is not yet known. The first-principles-based computational simulation was used to unveil the structure of 1' that shows the expansion in the framework, leading to pore opening after the removal of coordinated DMF molecules. We have used 1' that contains open metal sites (OMSs) in the structure in cyanosilylation and CO2 cycloaddition reactions and recorded complete conversions in a solventless setup. The pore opening in 1' allows the facile diffusion of small aldehyde molecules into the channels, leading to complete conversion. The reactions with larger aldehydes, 2-naphthaldehyde and 9-anthracenecarboxaldehyde, also show 99.9% conversions, which are the highest reported until date in solventless conditions. The in silico simulations illustrate that larger aldehydes interact with Mn(II) OMSs on the surfaces, enabling a closer interaction and facilitating complete conversions. The catalyst shows high recyclability, exhibiting 99.9% conversions in the successive reaction cycles with negligible change in the structure. Our investigations illustrate that the catalyst 1' is economical, efficient, and robust and allows reactions in a solventless greener setup, and therefore the catalysis with 1' can be regarded as "green catalysis".

Enhanced degradation of Congo-red dye by Cr3+ doped α-Fe2O3 nano-particles under sunlight and industrial wastewater treatment.

Considering the increasing amount of water pollution, nanocomposite advances for the effective elimination of hazardous pollutants are still needed. α-Fe2O3, Cr0·5Fe1·5O3 and CrFeO3 nanoparticles were synthesized via an eco-friendly material synthesis i. e hydrothermal route without using any precipitating agent and were studied to remove congo-red dye using photocatalytic properties. X-ray diffraction (XRD), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FESEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS) characterizations have been performed to know about the material structure and properties of synthesized samples. High efficiency (95.2%) of degradation was achieved under sunlight using a very low amount of CrFeO3 catalyst (0.2 g/L) at a 6-pH level of dye and was confirmed using UV spectroscopy, TOC (84%), LC-HRMS. Also, the potential to degrade the CR dye was concluded from the high rate of BOD5/COD. The results showed a significant enhancement in the degradation of α-Fe2O3 from 52.3% to 95.2% in a short duration of 15 min by introducing chromium as a dopant. The doping of chromium influenced the major factors responsible for the photocatalytic activity such as the increase in range of absorbance, increased e--h+ pair separation, improvement in the charge transfer process and active site formation which significantly enhanced the process of degradation. We found that the Cr-doped α-Fe2O3 nanomaterial could effectively remove dyes, such as congo-red, from industrial water-waste.

Metal-organic framework based drug delivery systems as smart carriers for release of poorly soluble drugs hydrochlorothiazide and dapsone.

Drug delivery systems (DDSs) that are derived from biocompatible carriers are attractive platforms for sustained release of drugs. In particular, sustained and controlled release of poorly soluble BCS (Biopharmaceutics Classification System) class IV drugs is important and this requires the development of new DDSs. In this work, we exploit two porous metal-organic frameworks (MOFs) MIL-100(Fe) and MIL-53(Fe) as carriers/DDSs for the release of two BCS class IV drugs hydrochlorothiazide (HCT) and dapsone (DAP). The chosen MOFs are known to possess good physicochemical stability and we realized high drug loading capacity that is attributed to the high porosity of the MOFs. The drug-encapsulated MOFs were characterized thoroughly and our results show ∼23.1% loading of HCT in MIL-100(Fe) and ∼27.6% loading of DAP in MIL-Fe(53), respectively. The release study of these drugs was carried out under simulated physiological conditions that shows sustained release of the drug molecules from the MOFs up to 72 h. Cell viability studies through MTT assays show insignificant cytotoxicity signalling biocompatibility of the proposed DDSs. Our investigations suggest MIL-100(Fe) and MIL-53(Fe) are potential DDSs for enhancing the performance of poorly soluble drugs HCT and DAP.

Biocompatible Drug Delivery System Based on a MOF Platform for a Sustained and Controlled Release of the Poorly Soluble Drug Norfloxacin.

Norfloxacin (NFX), an important antibacterial fluoroquinolone, is a class IV drug according to the biopharmaceutics classification system (BCS) and has low solubility and permeability issues. Such poor physicochemical properties of drug molecules lead to poor delivery and are of serious concern to the pharmaceutical industry for clinical development. We present here a conceptually new approach to deliver NFX, by loading the drug molecule on the porous platform of a biocompatible metal-organic framework (MOF), MIL-100(Fe). The loading of the drug on the MOF leading to NFX@MIL-100(Fe) was characterized by Fourier transform infrared (FTIR), UV-visible spectroscopy, thermogravimetric analyses (TGA), and nitrogen adsorption studies. Controlled experiments resulted in the high loading of the drug molecule (∼20 wt %) along with the desired sustained release. We could further control the release of norfloxacin by coating drug-loaded MIL-100(Fe) with PEG, PEG{NFX@MIL-100(Fe)}. Both drug delivery systems (DDSs), NFX@MIL-100(Fe) and PEG{NFX@MIL-100(Fe)}, were tested for their biocompatibility through toxicity studies. The DDSs are biocompatible and show insignificant cytotoxicity, as revealed by cell viability studies through the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay.

Open metal site (OMS)-inspired investigation of adsorption and catalytic functions in a porous metal-organic framework (MOF).

In this article, we report the adsorption and catalytic study of the three-dimensional (3D) metal-organic framework (MOF) {Mn2(1,4-bdc)2(DMF)2} (1) (1,4-bdcH2, 1,4-benzene dicarboxylic acid; DMF, N,N-dimethylformamide) together with the synthesis and structure of two new Mn(II)-MOFs {Mn3(Br-bdc)3(DMF)4} (2) and {Mn3(NO2-bdc)3(DMF)4} (3) (Br-bdcH2, 2-bromo-1,4-benzene dicarboxylic acid; NO2-bdcH2, 2-nitro-1,4-benzene dicarboxylic acid) under solvothermal conditions. Compounds 2 and 3 have two-dimensional (2D) extended structures and feature trimeric {Mn3(CO2)6} units that serve as secondary building units for the frameworks. The desolvated compound of 1, denoted as 1', having potential Mn(II) open metal sites (OMSs) lined in a one-dimensional (1D) Mn-chain interconnected by carboxylate groups, exhibits guest-selective adsorption of solvent vapours wherein the compound shows a stepwise profile with H2O vapour, while a gated isotherm was recorded with MeOH. After realizing the favourable interaction of 1' with polar solvent molecules, we have used Mn(II) OMSs in 1' for efficient cyanosilylation reactions of aromatic aldehydes. We have recorded 100% conversion for eight aromatic aldehydes, while several other aldehydes showed appreciable conversion. Notably, the recorded conversions in the case of many substrates are higher than those for many other reported MOF catalysts.