Metal–organic frameworks (MOFs), also known as coordination polymers, are formed by the self-assembly of metallic centres and bridging organic linkers. In this critical review, we review the key advances in the field and discuss the relationship between the nature and structure of specifically designed organic linkers and the properties of the products. Practical examples demonstrate that the physical and chemical properties of the linkers play a decisive role in the properties of novel functional MOFs. We focus on target materials suitable for the storage of hydrogen and methane, sequestration of carbon dioxide, gas separation, heterogeneous catalysis and as magnetic and photoluminescent materials capable of both metal- and ligand-centred emission, ion exchangers and molecular sieves. The advantages of highly active discrete complexes as metal-bearing ligands in the construction of MOFs are also briefly reviewed (128 references).

Antimicrobial photodynamic therapy (aPDT) has emerged in the clinical field as a potential alternative to antibiotics to treat microbial infections. No cases of microbial viability recovery or any resistance mechanisms against it are yet known. 5,10,15-tris(1-Methylpyridinium-4-yl)-20-(pentafluorophenyl)-porphyrin triiodide (Tri-Py⁺-Me-PF) was used as photosensitizer. Vibrio fischeri and recombinant Escherichia coli were the studied bacteria. To determine the bacterial recovery after treatment, Tri-Py⁺-Me-PF (5.0 µM) was added to bacterial suspensions and the samples were irradiated with white light (40 W m^-2) for 270 minutes. Then, the samples were protected from light, aliquots collected at different intervals and the bioluminescence measured. To assess the development of resistance after treatment, bacterial suspensions were exposed to white light (25 minutes), in presence of 5.0 μM of Tri-Py⁺-Me-PF (99.99% of inactivation) and plated. After the first irradiation period, surviving colonies were collected from the plate and resuspended in PBS. Then, an identical protocol was used and repeated ten times for each bacterium. The results suggest that aPDT using Tri-Py⁺-Me-PF represents a promising approach to efficiently destroy bacteria since after a single treatment these microorganisms do not recover their viability and after ten generations of partially photosensitized cells neither of the bacteria develop resistance to the photodynamic process.

Background: In recent times photodynamic antimicrobial therapy has been used to efficiently destroy Gram (+) and Gram (-) bacteria using cationic porphyrins as photosensitizers. There is an increasing interest in this approach, namely in the search of photosensitizers with adequate structural features for an efficient photoinactivation process. In this study we propose to compare the efficiency of seven cationic porphyrins differing in meso-substituent groups, charge number and charge distribution, on the photodynamic inactivation of a Gram (+) bacterium (Enterococcus faecalis) and of a Gram (-) bacterium (Escherichia coli). The present study complements our previous work on the search for photosensitizers that might be considered good candidates for the photoinactivation of a large spectrum of environmental microorganisms. Results: Bacterial suspension (10⁷ CFU mL^-1) treated with different photosensitizers concentrations (0.5, 1.0 and 5.0 μM) were exposed to white light (40 W m^-2) for a total light dose of 64.8 J cm^-2. The most effective photosensitizers against both bacterial strains were the Tri-Py⁺-Me-PF and Tri-Py⁺-Me-CO₂Me at 5.0 μM with a light fluence of 64.8 J cm^-2, leading to > 7.0 log (> 99,999%) of photoinactivation. The tetracationic porphyrin also proved to be a good photosensitizer against both bacterial strains. Both di-cationic and the monocationic porphyrins were the least effective ones. Conclusion: The number of positive charges, the charge distribution in the porphyrins' structure and the meso-substituent groups seem to have different effects on the photoinactivation of both bacteria. As the Tri-Py⁺-Me-PF porphyrin provides the highest log reduction using lower light doses, this photosensitizer can efficiently photoinactivate a large spectrum of environmental bacteria. The complete inactivation of both bacterial strains with low light fluence (40 W m^-2) means that the photodynamic approach can be applied to wastewater treatment under natural light conditions which makes this technology cheap and feasible in terms of the light source.

New hexapyrrolic macrocycles have been synthesized and characterized by UV–VIS, mass and NMR spectroscopy and X-ray crystallography.