Gold-Nanoparticle-Decorated Metal-Organic Frameworks for Anticancer Therapy

Confinement of Au nanoparticles (NPs) within the porous materials with few nanometers (2-3 nm) has been a well established research area in the past decades in heterogeneous catalysis mainly due to the unique behaviour of Au NPs than its bulk counterpart. In this aspect, Au NPs encapsulated within the pore volumes of metal−organic frameworks (MOFs) have been intensively explored as heterogeneous solid catalysts for wide range of reactions. In recent years, Au NPs confined within the porous MOFs along with the photosensitizer or drug have been effectively used for the treatment of tumor cells through the generation of reactive oxygen species via cascade reactions. This work highlights the benefits of MOFs pores in the preparation of nanomedicine with high efficiency by assembling Au NPs, photosensitizer/drug with the combination of laser either for imaging or treatment of tumor cells. Further, the existing literature is grouped based on the nature of porous materials employed in the preparation of nanomedicine. The final section comments on our view on future developments in the field.     

Application of an immobilized microbial consortium for the treatment of pharmaceutical wastewater: Batch-wise and continuous studies

In the present investigation, a microbial consortium consisting of four bacterial strains was selected for the treatment of pharmaceutical industry wastewater. The consortium was immobilized on a natural support matrix-Luffa and used for the treatment of real-time pharmaceutical wastewater in batch and continuous processes. The batch process was carried out to optimize the culture conditions and monitor the enzymatic activity. An array of enzymes such as alcohol dehydrogenase, aldehyde dehydrogenase, monooxygenase, catechol 2,3-dioxygenase and hydroquinol 1,2-dioxygenase were produced by the consortium. The kinetics of the degradation in the batch process was analyzed and it was noted to be a first-order reaction. For the continuous study, an aerobic fixed-film bioreactor (AFFBR) was utilized for a period of 61 days with variable hydraulic retention time (HRT) and organic loading rate (OLR). The immobilized microbes treated the wastewater by reducing the COD, phenolic contaminants and suspended solids. The OLR ranged between (0.56 ± 0.05) kg COD·m^-3 d^-1 to 3.35 kg COD·m^-3·d^-1 and the system achieved an average reduction of 96.8% of COD, 92.6% of phenolic compounds and 95.2% of suspended solids. Kinetics of the continuous process was interpreted by three different models, where the modified Stover Kincannon model and the Grau second-order model proved to be best fit for the degradation reaction with the constant for saturation value, KL being 95.12 g·L^-1·d^-1, the constant for maximum utilization of the substrate U_max being 90.01 g·L^-1 d^-1 and substrate removal constant K_Y was 1.074 d^-1 for both the models. GC-MS analysis confirmed that most of the organic contaminants were degraded into innocuous metabolites.     

Defects and Disorder in Covalent Organic Frameworks for Advanced Applications

Crystalline porous organic polymers (CPPs) or covalent organic frameworks (COFs), are composed by light elements linked by covalent bonds. Despite the remarkable progress attained, there are still bottlenecks limiting further development, some of them related to the presence of defects during their synthesis as well as in-depth understanding of structure of active centers and/or details of the reaction mechanism. Indeed, very often the proposed structures are far from reality because defects and disorders have not been considered. The present review provides an illustrative overview of “defects and disorder in COFs”. These defects include those not only generated during the synthesis and manipulation of COFs, but also lack of crystallinity, stacking disorder and network vacancies. The review starts giving general remarks on organic COFs and their synthetic methods, followed by different methods to play and manage defects, how to minimize them or how to take advantage of them to gain new properties and applications. Selected characterization techniques to quantify defective structures and active sites in COFs are also presented. Finally, the challenges and future opportunities in the field have been summarized in the last section.     

Claisen–Schmidt Condensation Catalyzed by Metal‐Organic Frameworks

Metal‐organic framework [Fe(BTC) (BTC=1,3,5‐benzenetricarboxylic acid)] is a convenient heterogeneous catalyst for the carbon‐carbon bond forming reaction in toluene between acetophenone and benzaldehyde to give selectively chalcone in high yield. Fe(BTC) appears as a general catalyst able to synthesize selectively different chalcone derivatives bearing various functionalities. Fe(BTC) could be recycled with no significant loss of catalytic efficiency and crystallinity in subsequent runs.     

Metal Organic Frameworks as Solid Acid Catalysts for Acetalization of Aldehydes with Methanol

Room temperature acetalization of aldehydes with methanol has been carried out using metal organic frameworks (MOFs) as solid heterogeneous catalysts. Of the MOFs tested, a copper‐containing MOF [Cu₃(BTC)₂] (BTC=1,3,5‐benzenetricarboxylate) showed better catalytic activity than an iron‐containing MOF [Fe(BTC)] and an aluminium containing MOF [Al₂(BDC)₃] (BDC=1,4‐benzenedicarboxylate). The protocol was validated for a series of aromatic and aliphatic aldehydes and used to protect various aldehydes into commercially important acetals in good yields without the need of water removal. In addition, the reusability and heterogeneity of this catalytic system was demonstrated. The structural stability of MOF was further studied by characterization with powder X‐ray diffraction, Brunauer–Emmett–Teller surface area measurements and Fourier‐transformed infrared spectroscopic analysis of a deactivated catalyst used to convert a large amount of benzaldehyde. The performance of copper MOF as acetalization catalyst compares favourably with those of other conventional homogeneous and heterogeneous catalysts such as zinc chloride, zeolite and clay.     

2D Metal–Organic Frameworks as Multifunctional Materials in Heterogeneous Catalysis and Electro/Photocatalysis

Metal–organic frameworks (MOFs) are composed of particles with 3D geometry and are currently among the most widely studied heterogeneous catalysts. To further increase their activity, one of the recent trends is to develop related 2D materials with a high aspect ratio derived from a large lateral size and a small thickness. Here, the use of these 2D MOFs as catalysts, electrocatalysts, and photocatalysts is summarized, illustrating the advantages of these 2D materials compared to analogous 3D MOFs. The state of the art is summarized in tables and, when possible, pertinent turnover number (TON) and frequency (TOF) values. This enhanced activity of 2D MOFs derives from the accessibility of the active sites, the presence of a higher density of defects, and exchangeable coordination positions around the MOFs, as well as from their ability to form thin films on electrodes or surfaces. The importance of providing convincing evidence of the stability of 2D MOFs under reaction conditions and general characterization data of the used 2D material after catalysis is highlighted. In the last part, views regarding challenges in the field and new developments that can be expected are presented.     

A biomimetic mesoporous silica–polymer composite scaffold for bone tissue engineering

A biomimetic organic–inorganic composite system comprising of microspheres fabricated from combination of a biodegradable polymer poly(lactide-co-glycolide) (PLGA) and bioactive mesoporous silica (SBA-15) has been developed through sintering technique for bone regeneration applications. The morphological and structural properties of the SBA-15/PLGA composite scaffold were evaluated using electron microscopy and fourier transform infrared spectroscopy and the results showed spherical morphology and composite nature. The presence of mesopores in the silica was confirmed through nitrogen adsorption–desorption isotherms. The surface area and pore size of mesoporous silica were found to be 792 m² g^?1 and 3.7 nm, respectively. The thermal characteristics of the SBA-15/PLGA composites studied using thermogravimetry analysis shows a weight loss of around 80% with the degradation occurring at 324?°C. The prepared scaffold is also found to support the adhesion and proliferation of osteoblast cells. The expression of specific bone markers is significantly enhanced in the SBA-15/PLGA composite scaffold when compared with the pristine polymeric scaffold indicating the positive effect of mesoporous silica. Hence, these SBA-15/PLGA composite scaffolds can be explored further for bone regeneration applications.     

Chemical instability of Cu3(BTC)2 by reaction with thiols

In contrast to Fe(BTC) (BTC: 1,3,5-benzenetricarboxylate), the crystal structure of Cu₃(BTC)₂, a commercial metal organic framework widely used as solid catalyst, collapses when contacted with thiols under mild reaction conditions forming copper nanoparticles.