A simple and straightforward strategy for expedient access to benzoxazoles using chemically engineered 2D magnetic graphene oxide nanosheets as an eco-compatible catalyst.

Two-dimensional (2D) graphene oxide nanosheets serve as an excellent support material for immobilizing metal complexes to deal with the drawbacks of homogeneous catalysis. In this work, we report a magnetically retrievable graphene oxide (MGO) based copper nanocatalytic system that has been efficiently exploited for obtaining a series of pharmaceutically and biologically active benzoxazole scaffolds. The nanocatalyst was designed by covalent immobilization of dehydroacetic acid (DHA) onto a magnetic amino-silanized graphene oxide nanosupport which was accompanied by its metallation with copper acetate. The structure of the synthesized MGO hybrid material (Cu@DHA@APTES@MGO) was characterized by numerous physico-chemical techniques such as transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometry (VSM), elemental mapping, atomic absorption spectroscopy (AAS), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis and energy-dispersive X-ray fluorescence spectroscopy (ED-XRF). The fabricated architectures exhibited high efficiency for cyclization of 2-aminophenols and ß-diketones with wide substrate scope, excellent functional group tolerance, a higher conversion percentage (>98%) and a high turnover number (TON). The exceptional catalytic activity could be attributed to the 2D architecture of graphene oxide which provides space for trapping of reactants between 2D graphitic overlayers and metal surfaces and the reaction proceeds to afford benzoxazole products with moderate to excellent conversion percentages. Notably, this nanocomposite could be recovered easily through an external magnetic force and reused for multiple runs without any appreciable loss in its catalytic efficacy.

Preparation and characterization of the h-BN/Fe3O4/APTES-AMF/CuII nanocomposite as a new and efficient catalyst for the one-pot three-component synthesis of 2-amino-4-aryl(or heteroaryl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles.

The intriguing features of surface-engineered hexagonal two-dimensional boron nitride (h-BN) nanostructures have captivated the immense interest of researchers working in the arena of materials science. Inspired by striking attributes exhibited by h-BN nanosheets as the support material, we devoted our efforts towards synthesizing a novel magnetically retrievable h-BN/Fe3O4/APTES-AMF/CuII catalytic system, which was then comprehensively characterized using various techniques including SEM, TEM, EDX, SEM-based elemental mapping, ED-XRF, AAS, XRD, FT-IR, VSM, XPS, TGA, and BET. Further, the catalytic potential of h-BN/Fe3O4/APTES-AMF/CuII nanocomposites was investigated in the one-pot multicomponent coupling reaction to gain access to a library of biologically active 2-amino-4-aryl(or heteroaryl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles under ambient conditions. In addition, the use of green solvent, facile magnetic recoverability, and reusability of up to six successive runs made this protocol environmentally benign and economical. This work throws light on the development of covalently functionalized 2D-BN nanostructure-based copper catalysts and establishes its significance in furnishing industrially demanding products that would pave the way towards sustainable chemistry.

An Earth-abundant cobalt based photocatalyst: visible light induced direct (het)arene C-H arylation and CO2 capture.

In this work, we have reported a noble metal free heterogeneous photocatalyst to carry out direct (het)arene C-H arylation and solvent-free CO2 capture via single-electron transfer processes at room temperature and under pressure. The catalytic system comprises a cobalt(III) complex grafted over the silica coated magnetic support for the efficient recovery of the photocatalytic moiety without hampering its light-harvesting capability. The novel Earth-abundant cobalt(III) based photocatalyst possesses various fascinating properties such as high surface area to volume ratios, large pore volume, crystalline behaviour, high metal loading, excellent stability and reusability. The general efficacy of the highly abundant and low-cost cobalt based heterogeneous nanocatalyst was checked for the selective conversion of aryldiazonium salts into synthetically and pharmaceutically significant biaryl motifs under ambient conditions upon irradiation with visible light. The highly efficient photocatalytic conversion of carbon dioxide (CO2) to a value-added chemical was accomplished under mild reaction conditions with high selectivity, showing the added benefit of operational simplicity.

Enhanced catalysis through structurally modified hybrid 2-D boron nitride nanosheets comprising of complexed 2-hydroxy-4-methoxybenzophenone motif.

Tuning the structural architecture of the pristine two dimensional hexagonal boron nitride (h-BN) nanosheets through rational surface engineering have proven advantageous in the fabrication of competent catalytic materials. Inspired by the performance of h-BN based nanomaterials in expediting key organic transformations, we channelized our research efforts towards engineering the inherent surface properties of the exclusively stacked h-BN nanosheets through the incorporation of a novel competent copper complex of a bidentate chelating ligand 2-hydroxy-4-methoxybenzophenone (BP). Delightfully, this hybrid nanomaterial worked exceptionally well in boosting the [3 + 2] cycloaddition reaction of azide and nitriles, providing a facile access to a diverse variety of highly bioactive tetrazole motifs. A deep insight into the morphology of the covalently crafted h-BN signified the structural integrity of the exfoliated h-BN@OH nanosheets that exhibited lamellar like structures possessing smooth edges and flat surface. This interesting morphology could also be envisioned to augment the catalysis by allowing the desired surface area for the reactants and thus tailoring their activity. The work paves the way towards rational design of h-BN based nanomaterials and adjusting their catalytic potential by the use of suitable complexes for promoting sustainable catalysis, especially in view of the fact that till date only a very few h-BN nanosheets based catalysts have been devised.

Silver nanomaterials: synthesis and (electro/photo) catalytic applications.

In view of their unique characteristics and properties, silver nanomaterials (Ag NMs) have been used not only in the field of nanomedicine but also for diverse advanced catalytic technologies. In this comprehensive review, light is shed on general synthetic approaches encompassing chemical reduction, sonochemical, microwave, and thermal treatment among the preparative methods for the syntheses of Ag-based NMs and their catalytic applications. Additionally, some of the latest innovative approaches such as continuous flow integrated with MW and other benign approaches have been emphasized that ultimately pave the way for sustainability. Moreover, the potential applications of emerging Ag NMs, including sub nanomaterials and single atoms, in the field of liquid-phase catalysis, photocatalysis, and electrocatalysis as well as a positive role of Ag NMs in catalytic reactions are meticulously summarized. The scientific interest in the synthesis and applications of Ag NMs lies in the integrated benefits of their catalytic activity, selectivity, stability, and recovery. Therefore, the rise and journey of Ag NM-based catalysts will inspire a new generation of chemists to tailor and design robust catalysts that can effectively tackle major environmental challenges and help to replace noble metals in advanced catalytic applications. This overview concludes by providing future perspectives on the research into Ag NMs in the arena of electrocatalysis and photocatalysis.

Aldehydes: magnificent acyl equivalents for direct acylation.

From the viewpoint of meeting the current green chemistry challenges in chemical synthesis, there is a need to disseminate how the cocktail of acylation and activation can play a pivotal role in affording bioactive acylated products comprising substituted ketone motifs in fewer reaction steps, with higher atom-economy and improved selectivity. In recent years, a significant number of articles employing the title compounds "aldehydes" as magnificent acylation surrogates which are less toxic and widely applicable have been published. This review sheds light on the compounds use for selective acylation of arene, heteroarene and alkyl (sp3, sp2 and sp) C-H bonds by proficient utilization of the C-H activation strategy. Critical insights into selective acylation of diverse moieties for the synthesis of bioactive compounds are presented in this review that will enable academic and industrial researchers to understand the mechanistic aspects involved and fruitfully employ these strategies in designing novel molecules.

Harnessing the Untapped Catalytic Potential of a CoFe2O4/Mn-BDC Hybrid MOF Composite for Obtaining a Multitude of 1,4-Disubstituted 1,2,3-Triazole Scaffolds.

Metal-organic frameworks derived nanostructures with extraordinary variability, and many unprecedented properties have recently emerged as promising catalytic materials to address the challenges in the field of modern organic synthesis. In this contribution, the present work reports the fabrication of an intricately designed magnetic MOF composite based on Mn-BDC (manganese benzene-1,4-dicarboxylate/manganese terephthalate) microflakes via a facile and benign in situ solvothermal approach. Structural information about the as-synthesized hybrid composite has been obtained with characterization techniques such as TEM, SEM, XRD, FT-IR, AAS, EDX, ED-XRF, and VSM analysis. Upon investigation of catalytic performance, the resulting material unveils remarkable efficacy toward facile access of a diverse array of pharmaceutically active 1,2,3-triazoles from a multicomponent coupling reaction of terminal alkynes, sodium azide, and alkyl or aryl halides as coupling partners. In addition to a wide substrate scope, the catalyst with highly accessible active sites also possesses a stable catalytic metal center along with superb magnetic properties that facilitate rapid and efficient separation. The prominent feature that makes this protocol highly desirable is the ambient and greener reaction conditions in comparison to literature precedents reported to date. Further, a plausible mechanistic pathway is also proposed to rationalize the impressive potential of the developed catalytic system in the concerned reaction. We envision that findings from our study would not only provide new insights into the judicious design of advanced MOF based architectures but also pave the way toward greening of industrial manufacturing processes to tackle critical environmental and economic issues.

Triptycene-Based and Schiff-Base-Linked Porous Networks: Efficient Gas Uptake, High CO2/N2 Selectivity, and Excellent Antiproliferative Activity.

A set of unique triptycene-based and organic Schiff-base-linked polymers (TBOSBLs) are conveniently synthesized in which triptycene motifs are connected with 1,3,5-triformylphloroglucinol units via Schiff-base linkages. TBOSBLs are amorphous, thermally stable with a reasonable surface area (SABET up to 649 m2/g), and have abundant nanopores (pore size < 100 nm). TBOSBLs are good sorbents for small gas molecules (such as CO2, H2, and N2) and they can selectively capture CO2 over N2. Additionally, TBOSBLs show superior antiproliferative activity against human colorectal cancer cells relative to previously reported covalent organic frameworks (COFs). The mechanism of cell death is also studied elaborately.

Design and Exploration of Catalytic Activity of Two-Dimensional Surface-Engineered Graphene Oxide Nanosheets in the Transannulation of N-Heterocyclic Aldehydes or Ketones with Alkylamines.

In this work, pharmaceutically and biologically important compounds containing imidazo[1,5-a]pyridine nuclei have been synthesized via transannulation of N-heteroaryl aldehydes or ketones with alkylamines using a graphene oxide-supported copper catalyst. The nanocatalyst was fabricated by the covalent immobilization of 4-aminoantipyrine onto an amine-functionalized graphene oxide nanosupport followed by its metallation with copper acetate. Structural analysis by transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction demonstrates that the two-dimensional sheet-like structure of graphene oxide is maintained even after the chemical modifications, whereas XPS revealed crucial information related to elemental composition and surface electronic states of the metal present in the catalyst. Apart from this, Fourier transform infrared spectroscopy helped in identifying the degree of oxidation and the presence of oxygenated groups in graphene oxide nanocomposites. As a heterogeneous catalyst, this graphene oxide-supported copper complex showed moderate to good catalytic activity in the C(sp3)-H bond activation/amination of a variety of substrates. This superior catalytic performance originated from the unique 2-dimensional structure of graphene oxide-based material which provided space between graphitic overlayers due to appropriate positioning of metal on their basal planes, decreasing the diffusion resistances of reactant surfaces, thus making it function as a nanoreactor. More importantly, this nanomaterial could be recovered easily and reused repeatedly by simple washing without chemical treatment with no appreciable loss in its catalytic activity, showing good potential for increasing the overall turnover number of this synthetically useful catalyst.

Expanding the Horizon of Multicomponent Oxidative Coupling Reaction via the Design of a Unique, 3D Copper Isophthalate MOF-Based Catalyst Decorated with Mixed Spinel CoFe2O4 Nanoparticles.

This work discloses the first ever magnetically retrievable copper isophthalate-based metal-organic framework (MOF) decorated with surface-modified cobalt ferrite (CoFe2O4) nanoparticles that have been utilized as catalytic reactors for obtaining a relatively large number of biologically active benzimidazole scaffolds. A facile one-pot solvothermal approach was employed for obtaining spherical and monodisperse CoFe2O4 nanoparticles, which were subsequently modified using suitable protecting and functionalizing agents. Finally, these functionalized magnetic nanoparticles were anchored onto the three-dimensional copper isophthalate MOF via a covalent immobilization methodology. The exploitation of advanced microscopic tools such as transmission electron microscopy and scanning electron microscopy provided valuable insights into the morphology of the immobilized MOF. These results indicated that the surface-modified magnetic nanoparticles had grown onto the surface of copper-5-nitroisophthalic acid MOF. A greener C-H functionalization strategy that involves the multicomponent oxidative cross-coupling between two different set of amines (sp2-hybridized nitrogen-containing anilines and sp3-hybridized nitrogen-containing alkyl/aryl amine derivatives) and sodium azide has been incorporated to provide access to a broad spectrum of the value-added target benzimidazole moieties. It is interesting to note that this magnetic MOF-catalyzed protocol not only replaces toxic solvents with water, which is a green solvent, but also enhances the economic competitiveness since the magnetic catalyst can be readily recovered and recycled for eight consecutive runs.

Fabrication of Core-Shell-Structured Organic-Inorganic Hybrid Nanocatalyst for the Expedient Synthesis of Polysubstituted Oxazoles via Tandem Oxidative Cyclization Pathway.

The quest for designing efficient heterogeneous catalytic systems for tandem oxidative cyclization reactions has provided a great impetus to research efforts, as it enables the step-economic construction of complex heterocyclic molecules as well as confers the benefits of a facile catalytic recovery. In the present study, we disclose a new core-shell-structured organic-inorganic hybrid copper nanocatalyst fabricated via the covalent grafting of 2,2'-dipyridyl ketone ligand on amine-functionalized silica-encapsulated magnetite nanoparticles, followed by its metallation with cupric acetate for the tandem oxidative cyclization of amines and ß-ketoesters, leading to the production of biologically active polysubstituted oxazole moieties. This programmed catalytic protocol proceeds via the formation of intermolecular C-C and C-N bonds by single-step synthesis and accommodates a broad combination of reaction coupling partners.

Quinoline-2-carboimine copper complex immobilized on amine functionalized silica coated magnetite nanoparticles: a novel and magnetically retrievable catalyst for the synthesis of carbamates via C-H activation of formamides.

In the present study, we report the synthesis of a highly efficient and magnetically retrievable catalytic system (Cu-2QC@Am-SiO2@Fe3O4) through the covalent immobilization of quinoline-2-carboxaldehyde (2QC) on an amine functionalized silica coated ferrite nanosupport followed by metallation with copper acetate. The structure of the organic-inorganic hybrid nanomaterial has been confirmed using various physicochemical techniques such as Powder X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-Ray Spectroscopy (EDS), Energy Dispersive X-Ray Fluorescence Spectroscopy (ED-XRF), Atomic Absorption Spectroscopy (AAS), Inductively Coupled Plasma Spectroscopy (ICP) and Vibrating Sample Magnetometry (VSM). The resulting nanocatalyst exhibits a remarkable catalytic efficacy in the synthesis of industrially and pharmaceutically significant carbamates via the C-H activation of formamides under solvent free conditions. The most important attribute of the present methodology is that the catalyst can be recovered simply through an external magnetic force and reused several times without any significant deterioration in its activity. Furthermore, the heterogeneity test has been carried out in order to ensure the intrinsic stability of the nanostructured catalyst. The activity of the Cu-2QC@Am-SiO2@Fe3O4 nanocatalyst has been found to be far more superior in comparison with the literature precedents in terms of the product yield, cost and reusability of the catalyst. Besides, ambient reaction conditions, simple workup procedure, wide substrate scope and cost effectiveness are some of the other outstanding features of this protocol that make it economical and sustainable.

New water resistant biomaterial biocide film based on guar gum.

This work was aimed to develop water resistant biocide film from renewable resources for applications in food and water technology. Guar gum, a polymeric galactomannan, was intrinsically modified to a new guar gum benzamide. Benzoylation was carried out by benzoyl chloride reaction in water medium and a propyl amine spacer was used to impart a high degree of hydrophobicity. The new guar gum benzamide was resistant to water and soluble in non aqueous solvent like dimethyl sulfoxide. Cast films of thickness 0.162 mm had a breaking point tensile strength of 21.95 Mpa. The water vapor permeability of biomaterial film was 0.28 g mm kPa(-1)h(-1)m(-2) and water contact angle on evaporative surface was 90.35 degree. Qualitative and quantitative biocide activity of film was established against Salmonella enterica, Escherichia coli, Staphylococcus aureus and Bacillus subtilis. The new guar gum benzamide absorbed strongly in UV region.