Phosphomolybdic acid supported on magnetic poly calix[4]resorcinarene-EDTA-chitosan network as a recyclable catalyst for the synthesis of 5-aroyl-NH-1,3-oxazolidine-2-ones.

In this work, a novel procedure for immobilization of phosphomolybdic acid (PMA) on Magnetic polycalix[4]resorcinarene grafted to chitosan by EDTA (calix-EDTA-Cs) was reported. The heterogeneous nanocomposite (CoFe2O4@calix-EDTA-Cs@PMA) was applied an acid nanocatalyst for the synthesis of 5-aroyl-NH-1,3-oxazolidine-2-ones through the reaction of α-epoxyketones with sodium cyanate (NaOCN) in polyethylene glycol (PEG) as a green solvent under ultrasonic irradiation conditions. Some features of this work include quick reaction time, high reaction yield, easy separation of the catalyst, thermal stability, and eco-friendly.

Copper-decorated core-shell structured ordered mesoporous containing cobalt ferrite nanoparticles as high-performance heterogeneous catalyst toward synthesis of tetrazole.

The present work describes the synthesis of copper immobilization on CoFe2O4/MCM-41 as a catalyst, which is created by attaching copper and ligand (N-phenyl anthranilic acid (PA)) on the surface of CoFe2O4/MCM-41 (CoFe2O4/MCM-41/PA/Cu). The synthesized CoFe2O4/MCM-41 support and immobilized copper were identified by FTIR, TEM, VSM, SEM XRD, and nitrogen adsorption-desorption analysis. The results showed that MCM-41 silica was coated with magnetite nanoparticles and copper was successfully immobilized on this structure. The catalytic performance of synthesized catalyst was tested in the synthesis of tetrazole. It was shown that the solid catalyst exhibited a strong magnetic response and showed good catalytic activity in the synthesis of tetrazole. The catalytic test showed that copper supported on CoFe2O4/MCM-41 hybrid showed much better catalytic activity than copper supported on CoFe2O4, indicating that MCM-41 plays an important role in CoFe2O4/MCM-41 hybrid for the synthesis of tetrazole. Separation of the solid catalyst from the reaction mixture was easily performed by external magnetism without apparent mass loss. And the catalyst could be reused six times for the synthesis of heterogeneous tetrazole.

TiO2/porous carbon as a new nanocomposite and catalyst for the preparation of 4H-pyrimido[2,1-b]benzimidazoles.

A nano TiO2/porous carbon nanocomposite (TiO2/PCN) was designed by the pyrolysis of peanut shells as bio waste with nano titanium dioxide. In the presented nanocomposite, titanium dioxide is properly placed in the positions and pores of the porous carbon, so that it acts as an optimal catalyst in the nanocomposite structure. The structure of TiO2/PCN was studied by various analyses such as Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray Spectroscopy (EDX), scanning electron microscopy (SEM), SEM coupled EDX (SEM mapping), transmission electron microscopy (TEM), X-ray fluorescence (XRF) and BET. TiO2/PCN was successfully tested as a nano catalyst for the preparation of some 4H-pyrimido[2,1-b]benzimidazoles in high yields (90-97%) and short reaction times (45-80 min).

Evaluation of central-metal effect on anticancer activity and mechanism of action of isostructural Cu(II) and Ni(II) complexes containing pyridine-2,6-dicarboxylate.

Two Cu(II) (C1) and Ni(II) (C2) complexes were designed through the one-pot reaction of pyridine-2,6-dicarboxylic acid and 2-aminobenzimidazole respectively with copper(II) nitrate hexahydrate and nickel(II) nitrate hexahydrate. Both complexes were characterized by single-crystal X-ray diffraction and the distorted octahedral geometry was recognized for them. The MTT assay indicated that the complexes have a significant antiproliferative effect on BEL-7404 cells. IC50 values confirmed that C1 (IC50 = 0.56 µM) is several times more potent than C2 (IC50 = 5.13 µM). The similar cellular uptake of the complexes in mentioned cells led to this proposal that the production of ROS with different values can be the main reason for different cytotoxicity of the complexes. In this study, C1 and C2 caused BEL-7404 cells arrest at the G2/M and S phases, respectively. The expression of p53, Bax up-regulation, and Bcl-2 down-regulation and also activation of procaspase-9, and 3 indicated that apoptosis through a caspase-dependent mitochondrion pathway is a remarkable pathway in BEL-7404 cells treated by C1 while mechanistic studies proved that C2 induce death of BEL-7404 cells through the activation of RAGE/PI3KC3/Beclin 1 autophagic cell signaling pathway, more specifically. The cytostatic effect of the complexes in the BEL-7404 3D spheroid model was depicted.

Novel Tl(III) complexes containing pyridine-2,6-dicarboxylate derivatives with selective anticancer activity through inducing mitochondria-mediated apoptosis in A375 cells.

Three novel Tl(III) complexes (C1), (C2) and (C3) were synthesized using the one-pot reactions of pyridine dicarboxylic acid derivatives, 2-aminobenzimidazole and/or 4-aminopyridine, and also thallium(III) nitrate trihydrate metal salt. The structure of all three complexes was determined by the single-crystal X-ray diffraction. C1 and C2 were realized to be isostructural with disordered square anti-prismatic geometry and for C3 arrangement of the distorted tricapped triangular prism was proposed. Cyclic voltammetry measurements on the complexes exhibited that formal potential values are more positive for C1 (E0' 0.109 V) and C3 (E0' 0.244 V) compared to C2 (E0' -0.051 V), versus Ag/AgCl under argon. Moreover, cytotoxicity of the compounds was evaluated in vitro against two cancer cell lines including a human melanoma (A375), a human colon adenocarcinoma (HT29), and also one normal cell human foreskin fibroblast (HFF). The selective and potent cytotoxicity effect was exhibited by C1 and C3 on cancer cell lines. The apoptosis through a caspase-dependent mitochondrion pathway was confirmed by ROS production, MMP reduction, p53 activation, Bax up-regulation, and Bcl-2 down-regulation, cytochrome c release, procaspase-9, and 3 expression, for A375 cells treated to C1 and C3. According to similar cellular uptake of the complexes in A375 cell line, the generation of ROS was considered as an effective agent to justify the inhibition effect C1 and C3 on mentioned cells. Furthermore, arresting the cell cycle in the G2-M phase and inducing apoptosis were indicated by these two complexes.

Correction: Adhesive functionalized ascorbic acid on CoFe2O4: a core-shell nanomagnetic heterostructure for the synthesis of aldoximes and amines.

[This corrects the article DOI: 10.1039/D0RA08244A.].

Copper based on diaminonaphthalene-coated magnetic nanoparticles as robust catalysts for catalytic oxidation reactions and C-S cross-coupling reactions.

In this work, the immobilization of copper(ii) on the surface of 1,8-diaminonaphthalene (DAN)-coated magnetic nanoparticles provides a highly active catalyst for the oxidation reaction of sulfides to sulfoxides and the oxidative coupling of thiols to disulfides using hydrogen peroxide (H2O2). This catalyst was also applied for the one-pot synthesis of symmetrical sulfides via the reaction of aryl halides with thiourea as the sulfur source in the presence of NaOH instead of former strongly basic and harsh reaction conditions. Under optimum conditions, the synthesis yields of sulfoxides, symmetrical sulfides, and disulfides were about 99%, 95%, and 96% respectively with highest selectivity. The heterogeneous copper-based catalyst has advantages such as the easy recyclability of the catalyst, the easy separation of the product and the less wastage of products during the separation of the catalyst. This heterogeneous nanocatalyst was characterized by FESEM, FT-IR, VSM, XRD, EDX, ICP and TGA. Furthermore, the recycled catalyst can be reused for several runs and is economically effective.

A nickel nanoparticle engineered CoFe2O4/SiO2-NH2@carboxamide composite as a novel scaffold for the oxidation of sulfides and oxidative coupling of thiols.

The purpose of this work was to prepare a new Ni-carboxamide complex supported on CoFe2O4 nanoparticles (CoFe2O4/SiO2-NH2@carboxamide-Ni). The carboxamide host material unit generated cavities that stabilized the nickel nanoparticles effectively and prevented the aggregation and separation of these particles on the surface. This compound was appropriately characterized using FT-IR spectroscopy, FE-SEM, ICP-OES, EDX, XRD, TGA analysis, VSM, and X-ray atomic mapping. The catalytic oxidation of sulfides and oxidative coupling of thiols in the presence of the designed catalyst was explored as a highly selective catalyst using hydrogen peroxide (H2O2) as a green oxidant. The easy separation, simple workup, excellent stability of the nanocatalyst, short reaction times, non-explosive materials as well as appropriate yields of the products are some outstanding advantages of this protocol.

A nickel nanoparticle engineered CoFe2O4@GO-Kryptofix 22 composite: a green and retrievable catalytic system for the synthesis of 1,4-benzodiazepines in water.

A composite of Ni nanoparticles incorporated in Kryptofix 22 conjugated magnetic nano-graphene oxide, CoFe2O4@GO-K 22·Ni, was synthesized via the grafting of Kryptofix 22 moieties on the magnetic nano-graphene oxide surface, followed by reaction of the nanocomposite with nickel nitrate. The Kryptofix 22 host material unit cavities can stabilize the Ni nanoparticles effectively and prevent their aggregation and separation from the surface. Characterization of the catalysts by FT-IR, FE-SEM, TGA, ICP, EDX, XRD, VSM and BET aided understanding the catalyst structure and morphology. This catalyst was efficiently applied for the synthesis of 1,4-benzodiazepine derivatives. The main advantages of the method are mild reaction conditions, inexpensive catalyst, it is environmentally benign, has high to excellent yields and shorter reaction times. This organometallic catalyst can be easily separated from a reaction mixture and was successfully examined for six runs with a slight loss of catalytic activity.

Rice husk-SiO2 supported bimetallic Fe-Ni nanoparticles: as a new, powerful magnetic nanocomposite for the aqueous reduction of nitro compounds to amines.

This paper reports a novel green procedure for immobilization of bimetallic Fe/Ni on amorphous silica nanoparticles extracted from rice husk (RH-SiO2). The heterogeneous nanocomposite (Fe/Ni@RH-SiO2) was identified using SEM, EDX, TEM, BET, H2-TPR, TGA, XRD, VSM, ICP-OES, and FT-IR analyses. The Fe/Ni@RH-SiO2 nanocomposite was applied as a powerful catalyst for the reduction of structurally diverse nitro compounds with sodium borohydride (NaBH4) in green conditions. This procedure suggests some benefits such as green chemistry-based properties, short reaction times, non-explosive materials, easy to handle, fast separation and simple work-up method. The catalyst was separated by an external magnet from the reaction mixture and was reused for 9 successive cycles with no detectable changes of its catalytic efficiency.

Adhesive functionalized ascorbic acid on CoFe2O4: a core-shell nanomagnetic heterostructure for the synthesis of aldoximes and amines.

This paper reports on the simple synthesis of novel green magnetic nanoparticles (MNPs) with effective catalytic properties and reusability. These heterogeneous nanocatalysts were prepared by the anchoring of Co and V on the surface of CoFe2O4 nanoparticles coated with ascorbic acid (AA) as a green linker. The prepared nanocatalysts have been identified by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray atomic mapping, thermogravimetric analysis, X-ray powder diffraction, vibrating sample magnetometer analysis, coupled plasma optical emission spectrometry and Fourier transform infrared spectroscopy. The impact of CoFe2O4@AA-M (Co, V) was carefully examined for NH2OH·HCl oximation of aldehyde derivatives first and then for the reduction of diverse nitro compounds with sodium borohydride (NaBH4) to the corresponding amines under green conditions. The catalytic efficiency of magnetic CoFe2O4@AA-M (Co, V) nanocatalysts was investigated in production of different aldoximes and amines with high turnover numbers (TON) and turnover frequencies (TOF) through oximation and reduction reactions respectively. Furthermore, the developed environment-friendly method offers a number of advantages such as high turnover frequency, mild reaction conditions, high activity, simple procedure, low cost and easy isolation of the products from the reaction mixture by an external magnetic field and the catalyst can be reused for several consecutive runs without any remarkable decrease in catalytic efficiency.

Immobilized VO-Schiff Base Complex on Modified Graphene Oxide Nanosheets as an Efficient and Recyclable Heterogeneous Catalyst in Deep Desulfurization of Model Oil.

New heterogeneous catalyst was synthesized via covalent anchoring of oxovanadium(IV) complex of 5,5?-dibromobis(salicyledene)diethylenetriamine (VO[5-Br(Saldien)]) on the surface of chloro-modified graphene oxide (GO@CTS). The structure of the catalyst was investigated using different characterization techniques such as XRD, SEM, EDX, FT-IR, TG, DTA and ICP-AES analyses. The synthesized heterogeneous oxovanadium(IV) was an efficient catalyst for high yield and selective oxidation desulfurization (ODS) of dibenzothiophene (DBT) as a model oil using H2O2 as oxidant and formic acid as a promoter. The effects of the catalyst mass, reaction temperature and time, formic acid/H2O2 ratio and molar ratio of H2O2 to the total amount of sulfur (O/S) on oxidation desulfurization activity were investigated. Moreover, the prepared catalyst can be easily separated from the reaction mixture and reused six times without a significant loss of catalytic activity and selectivity.

Structures of CoII and ZnII complexes of the proton-transfer compound derived from pyrazine-2,3-dicarboxylic acid and piperazine.

The reaction of the proton-transfer compound piperazine-1,4-diium pyrazine-2,3-dicarboxylate 4.5-hydrate, C4H12N2(2+)·C6H2N2O4(2-)·4.5H2O or (pipzH2)(pyzdc)·4.5H2O (pyzdcH2 is pyrazine-2,3-dicarboxylic acid and pipz is piperazine), (I), with Zn(NO3)2·6H2O and CoCl2·6H2O results in the formation of bis(piperazine-1,4-diium) bis(µ-pyrazine-2,3-dicarboxylato)-κ(3)N(1),O(2):O(3);κ(3)O(3):N(1),O(2)-bis[aqua(pyrazine-2,3-dicarboxylato-κ(2)N(1),O(2))zinc(II)] decahydrate, (C4H12N2)2[Zn2(C6H2N2O4)4(H2O)2]·10H2O or (pipzH2)2[Zn(pyzdc)2(H2O)]2·10H2O, (II), and catena-poly[piperazine-1,4-diium [cobalt(II)-bis(µ-pyrazine-2,3-dicarboxylato)-κ(3)N(1),O(2):O(3);κ(3)O(3):N(1),O(2)] hexahydrate], {(C4H12N2)[Co(C6H2N2O4)2]·6H2O}n or {(pipzH2)[Co(pyzdc)2]·6H2O}n, (III), respectively. In (I), pyzdcH2 is doubly deprotonated on reaction with piperazine as a base. Compound (II) crystallizes as a dimer, whereas compound (III) exists as a one-dimensional coordination polymer. In (II), two pyzdc(2-) groups chelate to each of the two Zn(II) atoms through a ring N atom and an O atom of the 2-carboxylate group. In one ligand, the adjacent 3-carboxylate group bridges to a neighbouring metal atom. A water molecule ligates in the sixth coordination site. The structure of (II) can be described as a commensurate superlattice due to an ordering in the hydrogen-bonded network. In (III), no water is coordinated to the metal atom and the coordination sphere is comprised of two N,O-chelates plus two bridging O atoms. A large number of hydrogen bonds are observed in all three compounds. These interactions, as well as π-π and C=O...π stacking interactions, play important structural roles.

Piperazine-1,4-diium pyridine-2,3-dicarboxyl-ate methanol monosolvate.

The title solvated molecular salt, C(4)H(12)N(2) (2+)·C(7)H(3)NO(4) (2-)·CH(3)OH or (pipzH(2))(py-2,3-dc)·MeOH, was prepared by the reaction of pyridine-2,3-dicarb-oxy-lic acid (py-2,3-dcH(2)) and piperazine (pipz) in methanol (MeOH) as solvent. One of the two carboxylate groups of the acid fragment is nearly perpendicular to the pyridine ring and the other is almost in its plane [C-C-C-O torsion angles = -85.50 (11) and 88.07 (11)° and N-C-C-O torsion angles = -176.31 (8) and 5.41 (13)°]. In the crystal, the components are linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, generating a three-dimensional network.

Poly[[piperazine-1,4-dium [diaqua-tetra-kis-(µ-sulfanediyldiacetato)-dicerate(III)]] trihydrate].

The title compound, (C(4)H(12)N(2))[Ce(2)(C(4)H(4)O(4)S)(4)(H(2)O)(2)]·3H(2)O, features a polymeric anion with a centrosymmetric Ce(2)O(2) core and a Ce⋯Ce distance of 4.3625 (4) Å. The anions form ribbons {[Ce(2)(C(4)H(4)O(4)S)(4)(H(2)O)(2)](2-)}(n) extending along [100]. The doubly protonated piperazinium cations reside on centers of inversion and link the polymeric ribbons via N-H⋯O hydrogen bonding. Each Ce(III) cation is ten-coordinated by an O(2)S donor set from two tridentate sulfanediyldiacetate (tda) ligands, one water mol-ecule and three other tda O donors from adjacent {Ce(tda)(2)(H(2)O)} units in a distorted bicapped cubic environment. Additional O-H⋯O hydrogen bonding involving the coordinated and solvent water mol-ecules is also present. H atoms of the crystal water molecules could not be located and were not included in the refinement.

Statistically disordered short hydrogen bonds in (pipzH2)(cdoH)2 and a comparison with (pipzH2)(cdo)·H2O (pipz is piperazine and cdoH2 is chelidonic acid).

Two related proton-transfer compounds, namely piperazine-1,4-diium 4-oxo-4H-pyran-2,6-dicarboxylate monohydrate, C(4)H(12)N(2)(2+)·C(7)H(2)O(6)(2-)·H(2)O or (pipzH(2))(cdo)·H(2)O, (I), and piperazine-1,4-diium bis(6-carboxy-4-oxo-4H-pyran-2-carboxylate), C(4)H(12)N(2)(2+)·2C(7)H(3)O(6)(-) or (pipzH(2))(cdoH)(2), (II), were obtained by the reaction of 4-oxo-4H-pyran-2,6-dicarboxylic acid (chelidonic acid, cdoH(2)) and piperazine (pipz). In (I), both carboxyl H atoms of chelidonic acid have been transferred to piperazine to form the piperazine-1,4-diium ion. The structure is a monohydrate. All potential N-H donors are involved in N-H···O hydrogen bonds. The water molecule spans two anions via the 4-oxo group of the pyranose ring and a carboxylate O atom. The hydrogen-bonding motif is essentially two-dimensional. The structure is a pseudomerohedral twin. In the asymmetric unit of (II), the anion consists of monodeprotonated chelidonic acid, while the piperazine-1,4-diium cation is located on an inversion centre. The single carboxyl H atom is disordered in two respects. Firstly, the disordered H atom is shared equally by both carboxylic acid groups. Secondly, the H atom is statistically disordered between two positions on either side of a centre of symmetry and is engaged in a very short hydrogen-bonding interaction; the relevant O···O distances are 2.4549 (11) and 2.4395 (11) Å, and the O-H···O angles are 177 (6) and 177 (5)°, respectively. Further hydrogen bonding of the type N-H···O places the (pipzH(2))(2+) cations in pockets formed by the chains of (cdoH)(-) anions. In contrast with (I), the (pipzH(2))(2+) cations form hydrogen-bonding arrays that are perpendicular to the anions, yielding a three-dimensional hydrogen-bonding motif. The structures of both (I) and (II) also feature π-π stacking interactions between aromatic rings.

Hexa-kis-(dimethyl sulfoxide-κO)thallium(III) trinitrate.

The title compound, [Tl(C(2)H(6)OS)(6)](NO(3))(3), consists of six dimethyl sulfoxide (DMSO) mol-ecules coordinated to a Tl(III) atom, which lies on a axis, and three nitrate anions (3. symmetry) to neutralize the charge. The coordination polyhedron around the Tl(III) atom is octa-hedral, defined by six O atoms of the DMSO mol-ecules. In the crystal structure, C-H⋯O hydrogen bonds are observed. One of the nitrate groups exhibits half-occupation.

Hexaaqua-nickel(II) tetra-aqua-bis-(µ-pyridine-2,6-dicarboxyl-ato)bis-(pyridine-2,6-dicarboxyl-ato)trinickelate(II) octa-hydrate.

The title compound, [Ni(H(2)O)(6)][Ni(3)(C(7)H(3)NO(4))(4)(H(2)O)(4)]·8H(2)O, was obtained by the reaction of nickel(II) nitrate hexa-hydrate with pyridine-2,6-dicarb-oxy-lic acid (pydcH(2)) and 1,10-phenanothroline (phen) in an aqueous solution. The latter ligand is not involved in formation of the title complex. There are three different Ni(II) atoms in the asymmetric unit, two of which are located on inversion centers, and thus the [Ni(H(2)O)(6)](2+) cation and the trinuclear {[Ni(pydc)(2)](2)-µ-Ni(H(2)O)(4)}(2-) anion are centrosymmetric. All Ni(II) atoms exhibit an octa-hedral coordination geometry. Various inter-actions, including numerous O-H⋯O and C-H⋯O hydrogen bonds and C-O⋯π stacking of the pyridine and carboxyl-ate groups [3.570 (1), 3.758 (1) and 3.609 (1) Å], are observed in the crystal structure.

Phenyl-hydrazinium (6-carb-oxy-pyridine-2-carboxyl-ato)(pyridine-2,6-dicarboxyl-ato)cobaltate(II)-pyridine-2,6-dicarb-oxy-lic acid-water (1/1/3).

The asymmetric unit of the title compound, (C(6)H(9)N(2))[Co(C(7)H(3)NO(4))(C(7)H(4)NO(4))]·C(7)H(5)NO(4)·3H(2)O, contains one (6-carb-oxy-pyridine-2-carboxyl-ato)(pyridine-2,6-dicarboxyl-ato)cobaltate(II) anion, one phenyl-hydrazinium cation, one pyridine-2,6-dicarb-oxy-lic acid mol-ecule and three uncoordin-ated water mol-ecules, part of which are disordered. The Co(II) ion is coordinated by a pyridine-2,6-dicarboxyl-ate ion and a 6-carb-oxy-pyridine-2-carboxyl-ate ligand almost perpendicular to each other [the angle between the least-squares planes is 87.38 (4)°] and is surrounded by two O atoms and two N atoms in the equatorial plane and two O atoms in axial positions, resulting in a distorted octa-hedral coordination geometry. There is an extensive three-dimensional network of O-H⋯O and N-H⋯O hydrogen bonds, which link the components.

(Propane-1,3-diammonium) bis-(4-hydroxy-pyridine-2,6-dicarboxyl-ato-κO,N,O)zinc(II) 3.5-hydrate.

The asymmetric unit of the title compound, (C(3)H(12)N(2))[Zn(C(7)H(3)NO(5))(2)]·3.5H(2)O, contains two formula units. The compound consists of an anionic complex, a doubly protonated propane-1,3-diamine as a counter-ion and 3.5 uncoord-inated water mol-ecules. The coordination polyhedron around the Zn(II )atom is distorted octa-hedral, defined by four O atoms and two N atoms from two Hchel (H(3)chel = 4-hydroxy-pyridine-2,6-dicarboxylic acid) ligands. In the crystal structure, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds along with π-π stacking inter-actions [centroid-centroid distance = 3.473 (2) Å] are observed to reinforce the crystal cohesion.