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.

BackgroundIn 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.ResultsBacterial 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.ConclusionThe 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.

Abstract-2-Styrylchromones are a small group of naturally occurring chromones, vinylogues of flavones (2-phenylchromones). Natural and synthetic 2-styrylchromones have been tested in different biological systems, showing activities with potential therapeutic applications. In particular, the potential and hitherto understudied antioxidant behavior of these compounds has been raised as a matter of interest. Thus the present work consisted in the study of the in vitro scavenging activities for reactive oxygen species (ROS) and reactive nitrogen species (RNS) of various 2-styrylchromone derivatives and structurally similar flavonoids. Some of the studied 2-styrylchromones proved to be extremely efficient scavengers of the different ROS and RNS, showing, in some cases, IC 50 s under 1 lM. The hydroxylation pattern of 2-styrylchromones, especially in the B-ring but also in the A ring, modulates the activity of these compounds, the catecholic derivatives being the most effective scavengers. The styryl pattern also contributes to their observed outstanding antioxidant activity. In conclusion, the scavenging activities for ROS/RNS of 2-styrylchromone derivatives, here shown for the first time, provide novel and most promising compounds to be applied as antioxidants.

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).

This review covers the functionalization reactions of meso-arylcorroles, both at the inner core, as well as the peripheral positions of the macrocycle. Experimental details for the synthesis of all known metallocorrole types and for the N-alkylation reactions are presented. Key peripheral functionalization reactions such as halogenation, formylation, carboxylation, nitration, sulfonation, and others are discussed in detail, particularly the nucleophilic aromatic substitution and the participation of corroles in cycloaddition reactions as 2π or 4π components (covering Diels-Alder and 1,3-dipolar cycloadditions). Other functionalizations of corroles include a large diversity of reactions, namely Wittig reactions, reactions with methylene active compounds, formation of amines, amides, and imines, and metal catalyzed reactions. At the final section, the reactions involving oxidation and ring expansion of the corrole macrocycle are described comprehensively.

Studies on the synthesis, structural elucidation, and biological evaluation of new conjugates of poly-S-lysine with meso-substituted porphyrins are described. The new conjugates were used in the photoinactivation of antibiotic-resistant Gram-positive bacteria (Staphylococcus aureus strains ATCC 25923 and MRSA 110) and Gram-negative bacteria (Escherichia coli strain O4). The results show that the cationic conjugates are able to photosensitize the efficient inactivation of both types of bacteria.

A core phthalocyanine platform allows engineering the solubility properties the band gap; shifting the maximum absorption toward the red. A simple method to increase the efficiency of heterojunction solar cells uses a self-organized blend of the phthalocyanine chromophores fabricated by solution processing.Low-cost photovoltaic (PV) devices may derive performance benefits from the light-absorbing properties of phthalocyanine organic dyes because of their high extinction coefficients, stability, and energy band gaps well-matched to the incident solar spectrum. [1][2][3][4] Despite these desirable attributes, use of phthalocyanines in low-cost solar cells is complicated by their poor solubility in organic solvents (necessitating vacuum deposition processing) 2,5,6 and narrow absorption bandwidths at red (Q-band) and ultraviolet (B-band) wavelengths. 7 Bulk heterojunction (BHJ) solar cells with dyes such as phthalocyanine 5,7,8 and polymer blends have been reported. 9,10 There are a several solar cell designs that contain phthalocyanines, especially the zinc and copper complexes, and those that also contain various C 60 derivatives wherein the layers are vapor-deposited in specified layers. [11][12][13] Other soluble dye systems have been incorporated into layered devices, or into BHJ solar cells. 4,[14][15][16] We demonstrate a new blend-type parallel tandem solar cell device architecture with several innovative features. (1) Click-type alkyation chemistry on a single commercially available phthalocyanine platform allows design of a series of robust, chemically compatible dyes with tunable optical band gaps and energy levels. (2) The family of soluble phthalocyanine dyes permits solution-based processing of molecular BHJ solar cells. (3) In these devices, the semiconductor active layer is composed of a blend of three phthalocyanine derivatives having The ca. 70 nm thick blended phthalocyanine active layer provides a disordered tandem device architecture wherein light can be absorbed by materials with successively smaller band gaps and photogenerated charges are collected with a common complementary organic semiconductor. This demonstrates that a hierarchical organization of dyes, wherein the lowest band gap (red) dye is at the surface and higher band gap (blue) dyes are layered or assembled on top, is not a priori necessary to assure vectoral charge migration between the electrodes. 2, 17 A standard, reproducible, solution-processed device architecture is used to illustrate these points. 9,11We achieve both improved phthalocyanine solubility and control over the optical properties using high yield substitution of peripheral fluoro groups on hexadecafluorophthalocyanato zinc (ZnPcF 16 ) by thio-alkanes (CH 3 (CH 2 ) 11 SH) (Scheme 1). 18,19 Because the frontier molecular orbitals (HOMO and LUMO) are primarily delocalized on the ring periphery, substitution of electron withdrawing groups with electron-donating groups affects the orbital energy levels. 5,7 The HOMO is destabilized more than the LUMO, resultin...

Photodynamic therapy has been used to inactivate microorganisms through the use of targeted photosensitizers. Recently the inactivation of bacteria in residual waters has been reported, but nothing is known about photoinactivation of environmental bacteriophages, which are often used as indicators of human enteric viruses. In this study we tested the effect of six cationic porphyrin derivatives with two to four charges on the photoinactivation of a sewage bacteriophage. A phage suspension of 5 x 10(7) PFU mL(-1) was exposed to white light (40 W m(-2)), during 270 min, at three photosensitizer concentrations (0.5, 1.0 and 5.0 microM). Tetra- and tricationic porphyrins inactivated the T4-like sewage phage to the limits of detection, but dicationic porphyrins did not lead to a significant decrease in phage viability. At the highest photosensitizer concentration (5.0 microM), the phage was completely inactivated (>99.9999% of inactivation, reduction of 7.2 log) after 270 min by the tetracationic porphyrin. Two of the tricationic derivatives also led to phage inactivation to the limit of detection. The rate of bacteriophage photoinactivation and the efficiency of the photosensitizer appeared to vary with the charge and with the substituents in the meso-positions of the porphyrin macrocycle. Tetra- and tricationic porphyrins can, therefore, be used as a new method for inactivating sewage bacteriophages that are frequently used as human enteric virus indicators. The complete inactivation of viruses with low light intensity means that this methodology can be used even on cloudy days and during winter, opening the possibility to develop new technologies for wastewater treatment.