Two new bioactive silver–organic frameworks [Ag(μ3-PTAS)]n(NO3)n·nH2O (1) and [Ag4(μ4-PTAS)(μ5-PTAS)(μ2-SO4)2(H2O)2]n·2nH2O (2) were easily assembled, thus opening up the application of PTAS as a versatile N,S-building block in the crystal engineering of MOFs. The obtained products reveal infinite 3D networks driven by multiply bridging PTAS spacers that adopt unprecedented N2S-coordination modes. The topological analysis of 1 discloses an uninodal 3-connected net with the srs (SrSi2) topology, whereas 2 features a pentanodal 3,4,5-connected net with a hitherto undocumented topology. Apart from representing the first MOFs derived from PTAS, the compounds 1 and 2 display notable antibacterial and antifungal activities.
The present study reports the synthesis, characterization, and crystal structure of a novel bioactive metal-organic framework, [Ag4(µ-PTA)2(µ3-PTA)2(µ4-pma)(H2O)2]n·6nH2O (bioMOF 1), which was assembled from silver(I) oxide, 1,3,5-triaza-7-phosphaadamantane (PTA), and pyromellitic acid (H4pma). This product was isolated as a stable microcrystalline solid and characterized by standard methods, including elemental analysis, 1H and 31P{1H} NMR and FTIR spectroscopy, and single crystal X-ray diffraction. The crystal structure of 1 disclosed a very complex ribbon-pillared 3D metal-organic framework driven by three different types of bridging ligands (µ-PTA, µ3-PTA, and µ4-pma4−). Various bioactivity characteristics of bioMOF 1 were investigated, revealing that this compound acts as a potent antimicrobial against pathogenic strains of standard Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria, as well as a yeast (Candida albicans). Further, 1 showed significant antiviral activity against human adenovirus 36 (HAdV-36). Finally, bioMOF 1 revealed high cytotoxicity toward an abnormal epithelioid cervix carcinoma (HeLa) cell line with low toxicity toward a normal human dermal fibroblast (NHDF) cell line. This study not only broadens the family of PTA-based coordination polymers but also highlights their promising multifaceted bioactivity.
The new, water soluble, aminomethylphosphines were synthesized from P(CH2OH)3 and alkylpiperazines: P(CH2N(CH2CH2)2NCH3)3 (1) and P(CH2N(CH2CH2)2NCH2CH3)3 (2). Described already in literature P(CH2N(CH2CH2)2O)3 (3) were also obtained. The spectroscopic 1H, 31P and 13C NMR analyses and crystallographic studies of 1, 2 and 3 demonstrate that all these compounds have similar structures and spectroscopic properties, which almost do not depend on aliphatic rings in the molecules. Heteroleptic copper(I) iodide complexes with phosphines mentioned above and 2,2′-bipyridine (bpy): [CuI(bpy)P(CH2N(CH2CH2)2NCH3)3] (1B), [CuI(bpy)P(CH2N(CH2CH2)2NCH2CH3)3] (2B), [CuI(bpy)P(CH2N(CH2CH2)2O)3] (3B) or 1,10-phenanthroline (phen): [CuI(phen)P(CH2N(CH2CH2)2NCH3)3] (1P), [CuI(phen)P(CH2N(CH2CH2)NCH2CH3)3] (2P), [CuI(phen)P(CH2N(CH2CH2)2O)3] (3P) were also synthesized. All complexes were characterized by 1H, 31P and 13C NMR spectroscopy also. Molecular structures of 1P·PhCH3 and 3P·0.5Cu2I2(phen)2 were determined from single crystal X-ray diffraction studies. Upon excitation at 470 nm, all complexes in the solid state exhibit red photoluminescence due to charge transfer transition. The luminescence of phen complexes is higher than the luminescence of bpy ones. The presented phosphines and copper(I) complexes were screened for their in vitro antibacterial and antifungal activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus strains and Candida albicans. All the copper complexes exhibit significant antibacterial activity against Staphylococcus aureus strains. The activity of 1,10-phenanthroline complexes is higher than 2,2′-bipyridine complexes.
31 August 2011 in Journal of Inorganic Biochemistry