Reusable Cavitand‐Based Electrospun Membranes for the Removal of Polycyclic Aromatic Hydrocarbons from Water

The removal of toxic and carcinogenic polycyclic aromatic hydrocarbons (PAHs) from water is one of the most intractable environmental problems nowadays, because of their resistance to remediation. This work introduces a highly efficient, regenerable membrane for the removal of PAHs from water, featuring excellent filter performance and pH-driven release, thanks to the integration of a cavitand receptor in electrospun polyacrylonitrile (PAN) fibers. The role of the cavitand receptor is to act as molecular gripper for the uptake/ release of PAHs. To this purpose, the deep cavity cavitand BenzoQxCav is designed and synthetized and its molecular structure is elucidated via X-Ray diffraction. The removal efficiency of the new adsorbent material toward the 16 priority PAHs is demonstrated via GC-MS analyses at ng L−1 concentration. A removal efficiency in the 32%, to 99% range is obtained. The regeneration of the membrane is performed by exploiting the pH-driven conformational switching of the cavitand between the vase form, where the PAHs uptake takes place, to the kite one, where the PAHs release occurs. The absorbance and regeneration capability of the membrane are successfully tested in four uptake/release cycles and the morphological stability

A mixed valent heterometallic Cu-II/Na-I coordination polymer with sodium-phenyl bonds

A mixed valent heterometallic Cu/Na coordination polymer (1) is generated by the reaction of a Schiff base ligand, (6,6′-(1E,1′E)-(2-hydroxypropane-1,3-diyl)bis(azan-1-yl-1-ylidene) bis(methan-1-yl-1-ylidene)bis(2-methoxyphenol)) with copper(ii) acetate and sodium perchlorate. In addition to the presence of alcohol oxygen-sodium coordination bonds, the single crystal X-ray structure reveals that the 1D coordination polymer is stabilised by the formation of phenyl-sodium η-bonds, face-to-face π-π contacts and Cu-π interactions. This journal i

Combined Approach of Mechanochemistry and Electron Crystallography for the Discovery of 1D and 2D Coordination Polymers

Mechanochemical synthesis is an attractive preparative method that combines a green approach with versatility, efficiency, and rapidity of reaction. However, it often yields microcrystalline materials, and their small crystal size is a major hindrance to structure elucidation with conventional single-crystal or powder X-ray diffraction methods. This work presents the novel approach of combining mechanochemistry with electron diffraction techniques to elucidate the crystal structure of metal−organic compounds of zinc(II) and copper(II) with 2,6-pyridinedicarboxylic acid and 4,4′-bipyridine

Effect of the addition of Al2O3, TiO2 and ZnO on the thermal, structural and luminescence properties of Er3+-doped phosphate glasses

Er-doped phosphate glasses were fabricated by melt-quenching technique. The changes in their thermal, structural and luminescence properties with the addition of Al2O3, TiO2 or ZnO were studied. Physical and thermal properties were investigated through density measurement and differential thermal analysis. Structural characterization was performed using the Raman and Infrared spectroscopy. In order to study the influence of the composition on the luminescence properties of the glasses, the refractive index, the luminescence spectra and the lifetime values were measured. The results show that with the addition of Al2O3 and TiO2 the phosphate network becomes more connected increasing the glass transition temperature, whereas the addition of ZnO does not show significant changes in the optical, thermal and structural properties but it leads to a larger emission cross-section at 1540 nm as compared to the other glasses. As the site of the Er3+ is not strongly affected by the change in the glass composition, we think that the emission properties of the glasses depend on the glass structure connectivity, which has an impact on the Er3+ ions solubility.Comment: 32 pages, 9 figures, 1 tabl

An enolato-bridged dinuclear Cu(II) complex with a coumarin-assisted precursor: a spectral, magnetic and biological study

Coumarin assisted dinuclear [Cu2(L)2(DMF)2] (1) shows weak ferromagnetic interaction and a geometric distortion occurs while lowering the temperature in EPR

A Ni(II) dinuclear complex bridged by end-on azide-N and phenolate-O atoms: spectral interpretation, magnetism and biological study

A new dinuclear complex, [Ni(L)(μ1,1-N3)Ni(L)(OH2)2]·ClO4(1), has been synthesized. It shows the presence of ferromagnetic interactions and is endowed with both anti-mycobacterial and anticancer properties

Nitrosonium complexation by the tetraphosphonate cavitand 5,11,17,23-tetramethyl-6,10:12,16:18,22:24,4-tetrakis(phenylphosphonato-κ2 O,O)resorcin(4)arene

The crystal structure of a new supramolecular complex between the tetraphosphonate cavitand 5,11,17,23-tetramethyl-6,10:12,16:18,22:24,4-tetrakis(phenylphosphonato- k2-2O,O0)resorcin(4)arene and the nitrosyl cation NO+, as the BF4 salt, is reported. The complex, of general formula [(C56H44P4O12)(NO)]BF4- CH2Cl2 or NO@Tiiii[H, CH3, C6H5] BF4CH2Cl2, crystallizes in the space group P1. The nitrosyl cation is disordered over two equivalent positions, with occupancies of 0.503 (2) and 0.497 (2), and interacts with two adjacent P O groups at the upper rim of the cavitand through dipole–charge interactions. In the lattice, the cavitands are connected through a series of C—H...pi interactions involving the methyl and methylenic H atoms and the aromatic rings of the macrocycle. The structure is further stabilized by the presence of C—H...F interactions between the hydrogen atoms of the cavitands and the F atoms of the tetrafluoridoborate anion. As a result of the disorder, the lattice dichloromethane molecules could not be modelled in terms of atomic sites, and were treated using the PLATON SQUEEZE procedure [Spek (2015). Acta Cryst. C71, 9–18]. The complexation process has also been studied in solution through NMR titration

Crystal structure of a host–guest complex between mephedrone hydrochloride and a tetraphosphonate cavitand

A new supramolecular complex (I) between the tetraphosphonate cavitand Tiiii[C3H7,CH3,C6H5] [systematic name: 2,8,14,20-tetrapropyl-5,11,17,23-tetramethyl-6,10:12,16:18,22:24,4-tetrakis(phenylphosphonato-O,O′)resorcin[4]arene] and mephedrone hydrochoride {C11H16NO+·Cl−; systematic name: methyl[1-(4-methylphenyl)-1-oxopropan-2-yl]azanium chloride} has been obtained and characterized both in solution and in the solid state. The complex of general formula (C11H16NO)@Tiiii[C3H7,CH3,C6H5]Cl·CH3OH or C11H16NO+·Cl−·C68H68O12P4·CH3OH, crystallizes in the monoclinic space group P21/c with one lattice methanol molecule per cavitand, disordered over two positions with occupancy factors of 0.665 (6) and 0.335 (6). The mephedrone guest interacts with the P=O groups at the upper rim of the cavitand through two charge-assisted N—H...O hydrogen bonds, while the methyl group directly bound to the amino moiety is stabilized inside the π basic cavity via cation...π interactions. The chloride counter-anion is located between the alkyl legs of the cavitand, forming C—H...Cl interactions with the aromatic and methylenic H atoms of the lower rim. The chloride anion is also responsible for the formation of a supramolecular chain along the b-axis direction through C—H...Cl interactions involving the phenyl substituent of one phosphonate group. C—H...O and C—H...π interactions between the guest and adjacent cavitands contribute to the formation of the crystal structure

Structural characterization of the supramolecular complex between a tetraquinoxaline-based cavitand and benzonitrile

The structural characterization is reported of the supramolecular complex between the tetraquinoxaline-based cavitand 2,8,14,20-tetrahexyl-6,10:12,16:18,22:24,4-O,O′-tetrakis(quinoxaline-2,3-diyl)calix[4]resorcinarene (QxCav) with benzonitrile. The complex, of general formula C84H80N8O8·2C7H5N, crystallizes in the space group P\overline{1} with two independent molecules in the asymmetric unit, displaying very similar geometrical parameters. For each complex, one of the benzonitrile molecules is engulfed inside the cavity, while the other is located among the alkyl legs at the lower rim. The host and the guests mainly interact through weak C—H...π, C—H...N and dispersion interactions. These interactions help to consolidate the formation of supramolecular chains running along the crystallographic b-axis direction