Facile Cu-MOF-derived Co3O4 mesoporous-structure as a cooperative catalyst for the reduction nitroarenes and dyes.

The present study describes the environmentally friendly and cost-effective synthesis of magnetic, mesoporous structure-Co3O4 nanoparticles (m-Co3O4) utilizing almond peel as a biotemplate. This straightforward method yields a material with high surface area, as confirmed by various characterization techniques. Subsequently, the utilization of m-Co3O4, graphene oxide (GO), Cu(II)acetate (Cu), and asparagine enabled the successful synthesis of a novel magnetic MOF, namely GO-Cu-ASP-m-Co3O4 MOF. This catalyst revealed remarkable stability that could be easily recovered using a magnet for consecutive use without any significant decline in activity for eight cycles in nitro compound reduction and organic dye degradation reactions. Consequently, GO-Cu-ASP-m-Co3O4 MOF holds immense potential as a catalyst for reduction reactions, particularly in the production of valuable amines with high industrial value, as well as for the elimination of toxic-water pollutants such as organic dyes.

Sulfonic acid-functionalized chitosan-metal-organic framework composite for efficient and rapid conversion of fructose to 5-hydroxymethylfurfural.

In pursuit of designing a bio-based catalyst for the dehydration of biomass (i.e., fructose) to 5-hydroxymethylfurfural, a novel catalytic composite was prepared by in-situ formation of an Al-based metal-organic framework in the presence of chitosan. To enhance the acidity of the as-prepared catalyst, it was sulfonated with chlorosulfonic acid. Various characterization techniques, including XRD, XPS, FTIR, SEM/EDX, TGA, and elemental mapping analysis were applied to validate the formation of the acidic composite. Fructose dehydration conditions were also optimized using Response Surface Method (RSM) and it was found that reaction in the presence of catalyst (23 wt%) in DMSO, at 110 °C for 40 min led to the formation of HMF in 97.1%. Noteworthy, the catalyst was recyclable and stable up to five runs with a minor reduction in its activity.

Sulfonic acid-functionalized k-carrageenan/Cr-based metal-organic framework: An efficient and recyclable catalyst for fructose conversion to 5-hydroxymethylfurfural.

A novel bio-based catalyst was developed by in-situ forming Chromium(III) (Cr)-based metal-organic framework, MIL-101(Cr), in the presence of k-carrageenan (k-Car) and followed by a post-synthetic modification to introduce additional -SO3H functional groups into the composite structure of k-Car/MIL-101(Cr). Different analyses were conducted to confirm the successful catalyst formation. The catalyst performance was evaluated in the solid acid catalyzed dehydration of fructose to 5-hydroxymethylfurfural. The Response Surface Method (RSM) optimization determined that employing 33 wt% of the catalyst at 105 °C for 40 min resulted in a remarkable 97.8 % yield. The catalyst demonstrated suitable recyclability, maintaining its catalytic efficiency over four cycles. Comparative studies with k-Car and the non-sulfonated composite highlighted the superior activity of the catalyst, emphasizing the synergy between the k-Car, MIL-101(Cr) and the influence of -SO3H post-functionalizing on the catalytic performance.

Clay-supported bio-based Lewis acid ionic liquid as a potent catalyst for the dehydration of fructose to 5-hydroxymthylfurfural.

Caffeine and halloysite nanoclay mineral that are bio-based compounds were utilized to synthesize a novel Lewis acid heterogeneous catalyst. To this aim, halloysite was functionalized with 2,4,6-trichloro-1,3,5-triazine and reacted with caffeine, which was then converted to ionic liquid via a reaction with ZnCl2. The catalyst was applied for promoting the dehydration of fructose to 5-hydroxymethylfurfural. To investigate the effects of the reaction variables, response surface methodology was used. The product was achieved in 98.5% in 100 min using a catalyst loading of 30 wt% at 100 °C. Moreover, the catalyst was recyclable up to six runs with slight zinc leaching. Comparison of the catalytic activity of the catalyst with that of halloysite and a control catalyst with one caffeine-based Lewis acid ionic liquid confirmed the superior activity of the former and the important role of 2,4,6-trichloro-1,3,5-triazine for increasing the number of the grafted caffeine and thus the acidic sites of the catalyst. A plausible reaction mechanism was proposed, and the activity of the catalyst for other carbohydrates was also studied. According to the results, this catalyst catalyzed the reaction of other substrates to furnish 5-hydroxymethylfurfural in low to moderate yields. According to the kinetic studies, the activation energy was estimated to be 22.85 kJ/mol.

Efficient oxidation of sulfides to sulfoxides catalyzed by heterogeneous Zr-containing polyoxometalate grafted on graphene oxide.

In this study, a tri-component composite named Zr/SiW12/GO was meticulously prepared through an ultrasonic-assisted method. This composite incorporates zirconium nanoparticles (Lewis acid), a negatively charged Keggin type polyoxometalate, and graphene oxide, and serves as a remarkable heterogeneous catalyst. The Keggin component plays multiple roles as reducing, encapsulating, and bridging agents, resulting in a cooperative effect among the three components that significantly enhances the catalytic activity. The catalytic performance of Zr/SiW12/GO was thoroughly investigated in the oxidation of sulfides to sulfoxides under mild conditions, employing H2O2 as the oxidant. Remarkably, this composite exhibited exceptional stability and could be effortlessly recovered and reused up to four times without any noticeable loss in its catalytic activity.

Ionothermal synthesis of magnetic N-doped porous carbon to immobilize Pd nanoparticles as an efficient nanocatalyst for the reduction of nitroaromatic compounds.

Carbon materials play important roles as catalysts or catalyst supports for reduction reactions owing to their high porosity, large specific surface area, great electron conductivity, and excellent chemical stability. In this paper, a mesoporous N-doped carbon substrate (exhibited as N-C) has been synthesized by ionothermal carbonization of glucose in the presence of histidine. The N-C substrate was modified by Fe3O4 nanoparticles (N-C/Fe3O4), and then Pd nanoparticles were stabilized on the magnetic substrate to synthesize an eco-friendly Pd catalyst with high efficiency, magnetic, reusability, recoverability, and great stability. To characterize the Pd/Fe3O4-N-C nanocatalyst, different microscopic and spectroscopic methods such as FT-IR, XRD, SEM/EDX, and TEM were applied. Moreover, Pd/Fe3O4-N-C showed high catalytic activity in reducing nitroaromatic compounds in water at ambient temperatures when NaBH4 was used as a reducing agent. The provided nanocatalyst's great catalytic durability and power can be attributed to the synergetic interaction among well-dispersed Pd nanoparticles and N-doped carbonaceous support.

Preparation of magnetic biochar functionalized by polyvinyl imidazole and palladium nanoparticles for the catalysis of nitroarenes hydrogenation and Sonogashira reaction.

Catalysts are essential materials in biotechnology, medicine, industry, and chemistry. On the other hand, recycling and using waste materials is important in economic efficiency and green chemistry. Thus, biochar was prepared from the stem and roots of the Spear Thistle to recover waste. After magnetizing the biochar, its surface was modified with polyvinyl imidazole. Finally, this modified biochar was decorated with Pd nanoparticles and used as a selective and recyclable nanocatalyst in the hydrogenation of nitroarenes and the Sonogashira reaction. The structure of this organic-inorganic nanocatalyst has been characterized by FESEM-EDS, XRD, FT-IR, TEM, and VSM techniques. In the hydrogenation reaction with the amount of 30 mg of nanocatalyst, the temperature of 50 °C in the water solvent, the reaction efficiency reached 99% for 30 min. In addition, under optimal conditions for the Sonogashira reaction: 1.0 mmol iodobenzene, 1.2 mmol phenylacetylene, 20 mg MBC-PVIm/Pd, 2 mmol K2CO3 in H2O at 50 C for 15 min, the reaction efficiency reached 95%. The recyclability of magnetic nanocatalysts was investigated and recognized this nanocatalyst can be used several times without notable loss of its activity.

Tuning the acidity of halloysite by polyionic liquid to develop an efficient catalyst for the conversion of fructose to 5-hydroxymethylfurfural.

In an attempt to prepare a low-cost and efficient acidic heterogeneous catalyst for the conversion of fructose to 5-hydroxymethylfurfural under mild reaction conditions, the acidity of halloysite was improved by covalent grafting of an acidic polyionic liquid. More precisely, halloysite was first vinyl functionalized and then polymerized with vinyl imidazole and 2-acrylamido-2-methylpropanesulfonic acid. The tangling imidazole rings were further converted to acidic ionic liquids by treating them with chlorosulfuric acid. UV-Vis spectroscopy and Hammett equation confirmed that conjugation of acid polyionic liquid resulted in the increase of the acidity of halloysite. Investigation of the efficiency of the catalyst for the synthesis of 5-hydroxymethylfurfural and optimization of reaction variables showed that 5-hydroxymethylfurfural was yielded in 97.8% after 30 min under the optimum conditions, i.e. catalyst loading of 20 wt% at 70 °C. Notably, the catalyst was highly reusable and it could be reused for at least seven reaction runs with insignificant loss of its activity. Furthermore, this catalyst could also promote the conversion of sucrose and maltose to give moderate yields of 5-hydroxymethylfurfural.

Magnetized chitosan hydrogel and silk fibroin, reinforced with PVA: a novel nanobiocomposite for biomedical and hyperthermia applications.

Herein, a multifunctional nanobiocomposite was designed for biological application, amongst which hyperthermia cancer therapy application was specifically investigated. This nanobiocomposite was fabricated based on chitosan hydrogel (CS), silk fibroin (SF), water-soluble polymer polyvinyl alcohol (PVA) and iron oxide magnetic nanoparticles (Fe3O4 MNPs). CS and SF as natural compounds were used to improve the biocompatibility, biodegradability, adhesion and cell growth properties of the nanobiocomposite that can prepare this nanocomposite for the other biological applications such as wound healing and tissue engineering. Since the mechanical properties are very important in biological applications, PVA polymer was used to increase the mechanical properties of the prepared nanobiocomposite. All components of this nanobiocomposite have good dispersion in water due to the presence of hydrophilic groups such as NH2, OH, and COOH, which is one of the effective factors in increasing the efficiency of hyperthermia cancer therapy. The structural analyzes of the hybrid nanobiocomposite were determined by FT-IR, XRD, EDX, FE-SEM, TGA and VSM. Biological studies such as MTT and hemolysis testing proved that it is hemocompatible and non-toxic for healthy cells. Furthermore, it can cause the death of cancer cells to some extent (20.23%). The ability of the nanobiocomposites in hyperthermia cancer therapy was evaluated. Also, the results showed that it can be introduced as an excellent candidate for hyperthermia cancer therapy.

Chitosan bead containing metal-organic framework encapsulated heteropolyacid as an efficient catalyst for cascade condensation reaction.

Using cyclodextrin and chitosan that are bio-based compounds, a novel bi-functional catalytic composite is designed, in which metal-organic framework encapsulated phosphomolybdic acid was incorporated in a dual chitosan-cyclodextrin nanosponge bead. The composite was characterized via XRD, TGA, ICP, BET, NH3-TPD, FTIR, FE-SEM/EDS, elemental mapping analysis and its catalytic activity was examined in alcohol oxidation and cascade alcohol oxidation-Knoevenagel condensation reaction. It was found that the designed catalyst that possess both acidic feature and redox potential could promote both reactions in aqueous media at 55 °C and various substrates with different electronic features could tolerate the aforementioned reactions to furnish the products in 75-95% yield. Furthermore, the catalyst could be readily recovered and recycled for five runs with slight loss of the catalytic activity. Notably, in this composite the synergism between the components led to high catalytic activity, which was superior to each component. In fact, the amino groups on the chitosan served as catalysts, while cyclodextrin nanosponge mainly acted as a phase transfer agent. Moreover, measurement of phosphomolybdic acid leaching showed that its incorporation in metal-organic framework and bead structure could suppress its leaching, which is considered a drawback for this compound. Other merits of this bi-functional catalyst were its simplicity, use of bio-based compounds and true catalysis, which was proved via hot filtration.

Magnetic chitosan-silk fibroin hydrogel/graphene oxide nanobiocomposite for biological and hyperthermia applications.

This work represents a biocompatible magnetic nanobiocomposite prepared by the composition of chitosan (CS) hydrogel, silk fibroin (SF), graphene oxide (GO), and Fe3O4 NPs. Terephthaloyl thiourea was applied as a cross-linking agent to cross-link the CS strings. The CS hydrogel/SF/GO/Fe3O4 nanobiocomposite with many characteristics, such as high structural uniformity, thermal stability, biocompatibility, and stability in an aqueous solution. Various characteristics of this novel magnetic nanobiocomposite were distinguished by FT-IR, EDX, FE-SEM, XRD, TGA, and VSM analysis. The FE-SEM images were taken to evaluate the size distribution of the magnetic nanoparticles (MNPs) between 39.9 and 73.3 nm as well. The performance of the prepared nanobiocomposite was assessed by the magnetic fluid hyperthermia process. Under the alternating magnetic field (AMF), the mean value of the specific absorption rate (SAR) was determined at 43.15 w/g.

Ionic liquid-loaded triazine-based magnetic nanoparticles for promoting multicomponent reaction.

A novel hybrid magnetic ionic-liquid as a heterogeneous catalyst was synthesized by hybridization of imidazolium based-ionic liquid onto the nitrogen rich magnetic nanocomposite. The resulting catalyst (n-Fe3O4@SiO2-TA-SO3H IL) has two advantages besides recyclability: (i) high capacity of functional-SO3H group with imidazolium-IL cation for promoting symmetric and asymmetric Hantzsch reaction and (ii) easy recovery. Caused by the polymeric and magnetic nature of the n-Fe3O4@SiO2-TA-SO3H IL, large quantities of acidic groups were bound to the n-Fe3O4@SiO2-TA surface, which reduced the catalyst mass applied to the catalytic reaction. Moreover, superior catalytic performance and outstanding recyclability of n-Fe3O4@SiO2-TA-SO3H IL in mild condition make this method a green pathway for manufacture of satisfactory chemicals.

The preparation of polyvinyl imidazole-functionalized magnetic biochar decorated by silver nanoparticles as an efficient catalyst for the synthesis of spiro-2-Amino-4H-pyran compounds.

The silver nanoparticle was synthesized by developing poly (1-vinylimidazole) on the surface of magnetized biochar (the stem and roots of Spear Thistle) (biochar/Fe3O4/PVIm/Ag). This nanocomposite was characterized by Fourier-transformed infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). The SEM and TEM images of the nanocatalyst, biochar/Fe3O4/PVIm/Ag-NPs, confirmed the observation of microscopic sheets of biochar. The catalytic activity of these Ag NPs was tested via multicomponent reaction plus reusing to successful formation of 2-amino-4H-pyran and functionalized spirochromen derivatives. The prepared nanocatalyst was easily separated by an external magnet and reused in repeating coupling reaction cycles four times without remarkable activity loss. The catalyst showed great efficiency and reusability, thus making it an ideal candidate for catalytic purposes in several organic transformations.

Direction of theoretical and experimental investigation into the mechanism of n-HA/Si-PA-SC@Ag as a bio-based heterogeneous catalyst in the reduction reactions.

In the present study, a natural-based heterogeneous catalyst is synthesized. For this purpose, nano-hydroxyapatite (n-HA) is prepared, silica-modified and functionalized with phthalimide. Finally, Ag2+ was immobilized onto n-HA/Si-PA-SC and reduced to Ag nanoparticles by Bellis perennis flowers extract. n-HA/Si-PA-SC@Ag characterized by TGA, FTIR, SEM/EDX, XRD, TEM, BET and ICP-AES techniques. Moreover, metal-ligand interactions in n-HA/Si-PA-SC@Ag complex models were assessed to make a quantitative representation for the immobilization behavior of Ag NPs on the surface of n-HA/Si-PA-SC through quantum chemistry computations. Furthermore, the performance of n-HA/Si-PA-SC@Ag was studied in the nitroarene, methylene blue and congo red reductions. Finally, the recyclability study as well as Ag-leaching verified that, n-HA/Si-PA-SC@Ag was stable and reused-up to four times without losing its activity.

Heteroployacid on the composite of boehmite and polyionic liquid as a catalyst for alcohol oxidation and tandem alcohol oxidation Knoevenagel condensation reactions.

Using boehmite as an available and low-cost natural compound, a bi-functional catalytic composite is prepared through vinyl-functionalization of boehmite, followed by polymerization with the as-prepared bis-vinylimidazolium bromide ionic liquid and supporting of phosphotungstic acid. The catalyst was characterized via ICP, XRD, TGA, FTIR, SEM/EDS and elemental mapping analysis and applied for promoting alcohol oxidation reaction and one-pot tandem alcohol oxidation/Knoevenagel condensation reaction in aqueous media under mild reaction condition. The results indicated high catalytic activity of the catalyst for both reactions. This protocol showed high generality and aliphatic, aromatic and heterocyclic alcohols could be applied as substrates to furnish the corresponding products in high to excellent yields. Furthermore, hot filtration test confirmed true heterogeneous nature of the catalysis. The catalyst could also be recovered readily and reused for at least five runs of the reaction with low loss of the activity and phosphotungstic acid leaching upon each run.

Pd on cyclotriphosphazen-hexa imine decorated boehmite as an efficient catalyst for hydrogenation of nitro arenes under mild reaction condition.

Cyclotriphosphazen-hexa imine ligand was prepared through successive reactions of phosphonitrilchloride trimer with 4-hydroxybenzaldehyde and (3-aminopropyl) triethoxy silane. The as-prepared ligand was then covalently grafted on boehmite to furnish an efficient support for the immobilization of Pd nanoparticles and synthesis of a novel heterogeneous catalyst for hydrogenation of nitro arenes. The catalytic tests revealed that the catalyst had excellent catalytic activity for hydrogenation of various nitro arenes with different steric and electronic features under mild reaction condition in aqueous media. Noteworthy, the catalyst was highly selective and in the substrates with ketone or aldehyde functionalities, reduction of nitro group was only observed. The catalyst was also recyclable and only slight loss of activity was detected after each recycling run. Hot filtration test also approved true heterogeneous nature of catalysis.

Synthesis of Ag nanoparticles by Celery leaves extract supported on magnetic biochar substrate, as a catalyst for the reduction reactions.

Green synthesis of a noble metal such as Ag nanoparticles is an enormously developed research area. In this study, a biochar/Fe3O4-Ag magnetic nanocatalyst was produced via a green path by using Celery stalk as a carbon-based substrate and Celery leaf extract as reducing and stabilizing agents to construct Ag nanoparticles. The synthesized nanocatalyst was determined using various techniques, such as UV-Vis spectroscopy, FT-IR spectroscopy, XRD (X-ray diffraction), SEM/EDX spectroscopy (scanning electron microscopy/energy-dispersive X-ray), TEM (transmission electron microscopy), and VSM (vibrating sample magnetometer). To survey the catalytic action of the biochar/Fe3O4-Ag nanocatalyst, it was used in the reduction reaction of disparate nitroaromatics, aldehydes, and ketones. This catalyst has demonstrated good characteristics in terms of the amount, reusability, recoverability, activity, and structural integrity of the catalyst during the reaction. In addition, biochar/Fe3O4-Ag could be detached magnetically and recycled multiple times without significantly reducing its catalytic performance.

Incorporating heterogeneous lacunary Keggin anions as efficient catalysts for solvent-free cyanosilylation of aldehydes and ketones.

Polyoxometalates (POMs) as efficient catalysts can be used a wide range of chemical transformations due to their tunable Brønsted/Lewis-acidity and redox properties. Herein, we reported two hybrid and heterogeneous lacunary Keggin catalysts: (TBA)7[PW11O39] (TBA-PW11) and (TBA)8[SiW11O39]·4H2O (TBA-SiW11) (TBA+: tetrabutylammonium) in which [XW11O39]n- anions were coated by TBA+ cations. In this form, TBA+ can easily trap reactants on the surface of the catalysts and increase the catalytic reaction. Therefore, the catalytic performance of both POMs was tested in cyanosilylation of numerous compounds bearing-carbonyl group and trimethylsilyl cyanide under solvent-free conditions. TBA-PW11 is more effective than TBA-SiW11, conceivably due to the higher Lewis acidity of the P than the Si center and to the higher accessibility of the metal centers in the framework structure. Noteworthy, the recyclability and heterogeneity of both POMs catalysts were also examined, and the results confirmed that they remain active at least after three recycling procedures.

Lanthanoid-containing polyoxometalate nanocatalysts in the synthesis of bioactive isatin-based compounds.

Lanthanoid-containing polyoxometalates (Ln-POMs) have been developed as effective and robust catalysts due to their Lewis acid-base active sites including the oxygen-enriched surfaces of POM and the unique 4f. electron configuration of Ln. As an extension of our interest in Ln-POMs, a series of as-synthesized nanocatalysts K15[Ln(BW11O39)2] (Ln-B2W22, Ln = La, Ce, Nd, Sm, Gd, and Er) synthesized and fully characterized using different techniques. The Ln3+ ion with a big ionic radius was chosen as the Lewis acid center which is sandwiched by two mono-lacunary Keggin [BW11O39]9- units to form Ln-containing sandwiched type cluster. Consequently, the catalytic activity of nanocatalysts with different Ln was examined in the synthesis of bioactive isatin derivatives and compared under the same optimized reaction conditions in terms of yields of obtained products, indicating the superiority of the nano-Gd-B2W22 in the aforementioned simple one-pot reaction. The effects of different dosages of nanocatalyst, type of solvent, reaction time, and reaction temperature in this catalytic system were investigated and the best results were obtained in the presence of 10 mol% of nano-Gd-B2W22 in water for 12 min at the reflux condition.

Samarium(ii) iodide-mediated reactions applied to natural product total synthesis.

Natural product synthesis remains a field in which new synthetic methods and reagents are continually being evaluated. Due to the demanding structures and complex functionality of many natural products, only powerful and selective methods and reagents will be highlighted in this proceeding. Since its introduction by Henri Kagan, samarium(ii) iodide (SmI2, Kagan's reagent) has found increasing use in chemical synthesis. Over the years, many reviews have been published on the application of SmI2 in numerous reductive coupling procedures as well as in natural product total synthesis. This review highlights recent advances in SmI2-mediated synthetic strategies, as applied in the total synthesis of natural products since 2004.