SO3H-Functionalized Epoxy-Immobilized Fe3O4 Core-Shell Magnetic Nanoparticles as an Efficient, Reusable, and Eco-Friendly Catalyst for the Sustainable and Green Synthesis of Pyran and Pyrrolidinone Derivatives.

A SO3H-functionalized epoxy-immobilized Fe3O4 core-shell magnetic nanocatalyst was prepared through a simple three-step procedure, and it was identified by various analyses such as Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), differential thermal gravity (DTG), Brunauer-Emmett-Teller (BET) analysis, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), vibration sample magnetometry (VSM), and powder X-ray diffraction (PXRD). BET analysis showed that the as-prepared nanocatalyst was synthesized with a mesoporous structure and high specific area (35.45 m2 g-1). The TEM image clearly showed that the particle size distribution was in the range of 47-65 nm. The designed magnetic nanocatalyst was used successfully in the synthesis of pyran derivatives via the reaction of dimedone, malononitrile, and various aromatic aldehydes and synthesis of pyrrolidinone derivatives via the reaction of various aromatic aldehydes, aniline, and diethyl acetylenedicarboxylate. The nanocatalyst was simply isolated from the reaction mixture utilizing an external magnet and reused several times according to the model reactions without significant loss in its efficiency.

Picolylamine-Ni(ii) complex attached on 1,3,5-triazine-immobilized silica-coated Fe3O4 core/shell magnetic nanoparticles as an environmentally friendly and recyclable catalyst for the one-pot synthesis of substituted pyridine derivatives.

In the current study, an environmentally friendly and facile method was proposed for designing and constructing a catalyst with Ni(ii) attached to a picolylamine complex on 1,3,5-triazine-immobilized Fe3O4 core-shell magnetic nanoparticles (NiII-picolylamine/TCT/APTES@SiO2@Fe3O4) via a stepwise procedure. The as-synthesized nanocatalyst was identified and characterized via Fourier-transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), vibrating-sample magnetometry (VSM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), field-emission scanning electron microscopy (FE-SEM), inductively coupled plasma (ICP), and energy-dispersive X-ray spectrometry (EDX). The obtained results from the BET analysis indicated that the synthesized nanocatalyst had high specific area (53.61 m2 g-1) and mesoporous structure. TEM observations confirmed the particle size distribution was in the range 23-33 nm. Moreover, the binding energy peaks observed at 855.8 and 864.9 eV in the XPS analysis confirmed the successful and stable attachment of Ni(ii) on the surface of the picolylamine/TCT/APTES@SiO2@Fe3O4. The as-fabricated catalyst was used to produce pyridine derivatives by the one-pot pseudo-four component reaction of malononitrile, thiophenol, and a variety of aldehyde derivatives under solvent-free conditions or EG at 80 °C. The highest yield achieved was 97% for compound 4d in EG at 80 °C with a TOF of 823 h-1 and TON of 107. It was found that the used catalyst was recyclable for eight consecutive cycles. On the basis of ICP analysis, the results indicated that the Ni leaching was approximately 1%.

Electromembrane extraction using biodegradable deep eutectic solvents and agarose gel as green and organic solvent-free strategies for the determination of polar and non-polar bases drugs from biological samples: A comparative study.

Two modes of electromembrane extraction (EME) were evaluated in this work, one using deep eutectic solvents (DESs) as liquid membrane, and another was gel electromembrane extraction (G-EME) based on solid agarose membrane. Both EME modes have eliminated organic solvents and are recognized as green strategies. Unlike classic EME in which polypropylene membrane and organic extracting solvents play an essential role in the extraction process, new modes of EME are based on biodegradable membranes and aqueous extracting solutions. Approaches of EME based on the new designs follow the green chemistry principles. Each mode of EME was evaluated for the determination of polar and non-polar bases drugs from human urine samples using high-performance liquid chromatography (HPLC) equipped with a diode array detector (DAD). EME using DES A was suitable for determining polar and non-polar bases drugs in a large polarity window. While extraction recoveries for all six drugs studied by G-EME were lower than EME using DES A. Comparing the two EME modes shows similar results in the analytical figures of merit. However, differences in extraction recoveries of the drugs by two EME modes were observed which is related to the difference in membranes structure. Our findings indicate that the differences between membranes properties used in two EME modes, including the permeability, hydrophilicity, hydrophobicity, and variety of interactions, are influencer factors on extraction efficiency. The two EME modes provided good linearity in the ranges of 16-100 and 19-100 µg. L-1 for G-EME and EME using DES A, respectively with (r2 > 0.993). Also, the detection limits (LODs) were 19-32 and 19-29 µg. L-1 for G-EME and EME using DES A, respectively.

Magnetic Silica-Coated Picolylamine Copper Complex [Fe3O4@SiO2@GP/Picolylamine-Cu(II)]-Catalyzed Biginelli Annulation Reaction.

An efficient and heterogeneous novel magnetic silica-coated picolylaminecopper complex [Fe3O4@SiO2@GP/Picolylamine-Cu(II)] was synthesized, characterized, and employed as a magnetically recoverable nanocatalyst in Biginelli condensation for the preparation of biologically active 3,4-dihydropyrimidinones. Fe3O4@SiO2@GP/Picolylamine-Cu(II) was synthesized easily using chemical attachment of the picolylaminecompound on Fe3O4@SiO2@GP, followed by treatment with copper salt in ethanol under reflux conditions. Fe3O4@SiO2@GP/Picolylamine-Cu(II) was affirmed by various analyses such as Fourier transform infrared, thermogravimetric analysis, X-ray diffraction, vibrating-sample magnetometry, field-emission scanning electron microscopy, transmission electron microscopy, DLS, inductively coupled plasma, energy-dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller. The resulting catalyst system was successfully used in the Biginelli reaction through a variety of compounds such as aromatic aldehyde, urea, and ethyl acetoacetate under solvent-free conditions or ethylene glycol at 80 °C and yielded the desired products with high conversions with powerful reusability. The current approach was convenient and clean, and only 0.01 g of the catalyst could be used to perform the reaction. The easy work-up procedure, gram-scale synthesis, usage of nontoxic solvent, improved yield, short reaction times, and high durability of the catalyst are several remarkable advantages of the current approach. Also, the Fe3O4@SiO2@GP/Picolylamine-Cu(II) nanocatalyst could be recycled by an external magnet for eight runs with only a significant loss in the product yields.

Magnetic Nanoparticles Functionalized with Copper Hydroxyproline Complexes as an Efficient, Recoverable, and Recyclable Nanocatalyst: Synthesis and Its Catalytic Application in a Tandem Knoevenagel-Michael Cyclocondensation Reaction.

A novel catalyst has been afforded by attaching of a Cu(proline)2 complex to magnetic nanoparticles through cheap, simple, and readily available chemicals. This catalyst was characterized by Fourier transform infrared, energy-dispersive X-ray, X-ray diffraction, vibrating-sample magnetometry, transmission electron microscopy, scanning electron microscopy, and inductively coupled plasma analyses. The catalytic activity of the Fe3O4@NH2@TCT@HProCu nanocatalyst was investigated in a green and effective synthesis of pyran derivatives in high yields by applying three-component reactions of malononitrile, dimedone, and aldehydes in ethanol. Conversion was high under optimal conditions. The obtained nanocatalyst could be easily separated from the mixture of the reaction and was recyclable nine times via a simple magnet without considerable reduction of its catalytic efficiency. Operational simplicity, high product yields, environmental friendliness, ecofriendliness, economical processing, and easy workup are the features of this methodology.