Recyclable mesalamine-functionalized magnetic nanoparticles (mesalamine/GPTMS@SiO2@Fe3O4) for tandem Knoevenagel-Michael cyclocondensation: grinding technique for the synthesis of biologically active 2-amino-4H-benzo[b]pyran derivatives.

In the present study, mesalamine-functionalized on magnetic nanoparticles (mesalamine/GPTMS@SiO2@Fe3O4) is fabricated as an efficient and magnetically recoverable nanocatalyst. The as-prepared nanocatalyst was successfully synthesized in three steps using a convenient and low-cost method via modification of the surface of Fe3O4 nanoparticles with silica and GPTMS, respectively, to afford GPTMS@SiO2@Fe3O4. Finally, treatment with mesalamine as a powerful antioxidant generates the final nanocatalyst. Then, its structure was characterized by FT-IR, SEM, TEM, EDX, XRD, BET, VSM, and TGA techniques. The average size was found to be approximately 38 nm using TEM analysis and the average crystallite size was found to be approximately 27.02 nm using XRD analysis. In particular, the synthesized nanocatalyst exhibited strong thermal stability up to 400 °C and high magnetization properties. The activity of the synthesized nanocatalyst was evaluated in the tandem Knoevenagel-Michael cyclocondensation of various aromatic aldehydes, dimedone and malononitrile under a dry grinding method at room temperature to provide biologically active 2-amino-4H-benzo[b]pyran derivatives products in a short time with good yields. The presented procedure offers several advantages including gram-scale synthesis, good green chemistry metrics (GCM), easy fabrication of the catalyst, atom economy (AE), no use of column chromatography, and avoiding the generation of toxic materials. Furthermore, the nanocatalyst can be reused for 8 cycles with no loss of performance by using an external magnet.

Drug Delivery Using Hydrophilic Metal-Organic Frameworks (MOFs): Effect of Structure Properties of MOFs on Biological Behavior of Carriers.

To study the influence of pore structural properties of metal-organic frameworks (MOFs) on drug adsorption and delivery, we synthesized two MOF termed TMU-6(RL1) {[Zn(oba)(RL1)0.5]n·(DMF)1.5} and TMU-21(RL2) {[Zn(oba)(RL2)0.5]n·(DMF)1.5} with amine basic N-donor pillars containing phenyl or naphthyl cores with various hydrophilic properties around the main center of the reaction. TG, IR, XPS, and PXRD analyses were used to extensively characterize the MOFs. The synthesized carriers showed high adsorption efficiency, stability, and controlled release. As an anticancer drug, Nimesulide (Nim) was adsorbed to MOFs using multiple adsorption mechanisms, such as Hostπ-πGuest interaction and HostN-H···OGuest hydrogen bonds. Moreover, Hirshfeld surface analysis showed when the benzene core was replaced with the naphthalene core, the percentage of intermolecular interactions of π···π and N···H by amine sites in TMU-21(RL2) decreased compared with TMU-6(RL1), while the percentage of these interactions with guest molecules increased. The results showed that changes in the hydrophobicity/hydrophilicity properties of MOFs would alter their ability to adsorb Nim in the pore of the frameworks. In vitro anticancer studies also showed that the cytotoxicity of Nim in MOFs@Nim composites against human cervical cancer cell line (HeLa cells) and human colon cancer cell line (HT-29 cells) is much higher than that of free Nim. Generally, based on the results, it can be said that the biological behavior of carriers can be regulated by adjusting the structure properties of MOFs.

Synthesis of sterically congested 1,3,4-oxadiazole derivatives from aromatic carboxylic acids, N,N-dicyclohexylcarbodiimide and (N-isocyanimino)triphenylphosphorane.

Reactions of (N-isocyanimino)triphenylphosphorane with N,N-dicyclohexylcarbodiimide in the presence of aromatic (or heteroaromatic) carboxylic acids proceed smoothly at room temperature and in neutral conditions to afford sterically congested 1,3,4-oxadiazole derivatives in high yields. The reaction proceeds smoothly and cleanly under mild conditions, and no side reactions were observed.

A novel four-component reaction for the synthesis of disubstituted 1,3,4-oxadiazole derivatives.

The 1:1 imine intermediate generated by the addition of benzyl amine to cyclobutanone is trapped by (N-isocyanimino)triphenylphosphorane in the presence of an aromatic carboxylic acid leads to the formation of the corresponding iminophosphorane intermediate. Disubstituted 1,3,4-oxadiazole derivatives are formed via intramolecular aza-Wittig reaction of the iminophosphorane intermediate. The reactions were completed in neutral conditions at room temperature. The disubstituted 1,3,4-oxadiazole derivatives, were produced in excellent yields.