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Halophytic grasses have been recently targeted as possible sources of nutraceutical and medicinal compounds. Nonetheless, few studies have been conducted on the phytochemistry and biological activities of metabolites produced by these plants. Among these, Spartina maritima (Curtis) Fernald, Spartina patens (Aiton.) Muhl., and Puccinellia maritima (Hudson) Parl. are three halophytic grasses whose chemical composition and bioactivities are unknown. The present work broadens the knowledge on the polyphenolic and chlorophyll composition of these species identifying for the first time hydroxycinnamic acids and their derivatives, flavones, flavonols, lignans, as well as chlorophylls and xantophylls. The extracts were particularly rich in caffeic and ferulic acids as well as in trihydroxymethoxyflavone, apigenin and tricin derivatives. Interestingly, several of the identified compounds are relevant from a medicinal and nutraceutical point of view putting in evidence the potential of these species. Thus, the antioxidant, anti-acetylcholinesterase, antibacterial, and antifungal activities of the polyphenolic extracts were assessed as well as the photophysical properties of the chlorophyll-rich extracts. The results, herein presented for the first time, reinforce the nutritional and the medicinal potential of these halophytic grasses.

Anisakis spp. L3 larvae commonly found in marine fish species are an important biological hazard when raw or inadequately thermally processed fishery products are consumed with live larvae, highlighting the need for effective control strategies. This study evaluated the efficacy and mechanism of photodynamic inactivation (PDI) of Anisakis L3 larvae, using the cationic photosensitizer (PS) 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin tetraiodide (TMPyP). Larvae were collected from Atlantic horse mackerel and grouped by size: batch A (larvae ≈ 1.5 cm) and batch B (larvae ≈ 2.0 cm). Inactivation assays were performed in microcosms at 50 µM of TMPyP under different conditions: incubation times (15 min to 21 h); incubation temperatures (0.5 and 22 °C); irradiation period (2–8 h) and light irradiance (4, 14 and 67 mW/cm 2 ). Viability and tissue damage of the larvae were assessed at post-treatment. In both batches, 100% of larvae mortality was achieved after 21 h of dark incubation at 22 °C with TMPyP, followed by 6–8 h of white light irradiation at 67 mW/cm 2 . Similar results were observed in batch B, when the dark incubation was performed at 0.5 °C. Notably, batch B, larvae showed more exuberant cytotoxic effect, including severe damage of the intestinal epithelium, leading to loss of the characteristic triradiate appearance. These findings indicate that PDI using TMPyP is effective in inactivating Anisakis larvae and could be a potential alternative to freezing for ensuring the safety of fishery products in the food industry.

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 microM) 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 microM 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.

The development of new photodynamic therapy (PDT) agents designed for bladder cancer (BC) treatments is of utmost importance to prevent its recurrence and progression towards more invasive forms. Here, three different porphyrinic photosensitizers (PS) (TMPyP, Zn-TMPyP, and P1-C5) were non-covalently loaded onto graphene oxide (GO) or graphene quantum dots (GQDs) in a one-step process. The cytotoxic effects of the free PS and of the corresponding hybrids were compared upon blue (BL) and red-light (RL) exposure on T24 human BC cells. In addition, intracellular reactive oxygen species (ROS) and singlet oxygen generation were measured. TMPyP and Zn-TMPyP showed higher efficiency under BL (IC50: 0.42 and 0.22 μm, respectively), while P1-C5 was more active under RL (IC50: 0.14 μm). In general, these PS could induce apoptotic cell death through lysosomes damage. The in vitro photosensitizing activity of the PS was not compromised after their immobilization onto graphene-based nanomaterials, with Zn-TMPyP@GQDs being the most promising hybrid system under RL (IC50: 0.37 μg/mL). Overall, our data confirm that GO and GQDs may represent valid platforms for PS delivery, without altering their performance for PDT on BC cells.

Background: Photodynamic antimicrobial chemotherapy (PACT) combines light, a light-absorbing molecule that initiates a photochemical or photophysical reaction, and oxygen. The combined action of these three components originates reactive oxygen species that lead to microorganisms’ destruction. The aim was to evaluate the efficiency of PACT on Vibrio fischeri: 1) with buffer solution, varying temperature, pH, salinity and oxygen concentration values; 2) with aquaculture water, to reproduce photoinactivation (PI) conditions in situ. M e t h o d o l o g y / P r i n c i p a l F i n d i n g s : To monitor the PI kinetics, the bioluminescence of V. fischeri was measured during the experiments. A tricationic meso-substituted porphyrin (Tri-Py+-Me-PF) was used as photosensitizer (5 mM in the studies with buffer solution and 10–50 mM in the studies with aquaculture water); artificial white light (4 mW cm22) and solar irradiation (40 mW cm22) were used as light sources; and the bacterial concentration used for all experiments was <107 CFU mL21 (corresponding to a bioluminescence level of 105 relative light units - RLU). The variations in pH (6.5–8.5), temperature (10– 25uC), salinity (20–40 g L21) and oxygen concentration did not significantly affect the PI of V. fischeri, once in all tested conditions the bioluminescent signal decreased to the detection limit of the method (<7 log reduction). The assays using aquaculture water showed that the efficiency of the process is affected by the suspended matter. Total PI of V. fischeri in aquaculture water was achieved under solar light in the presence of 20 mM of Tri-Py+-Me-PF. Conclusions/Significance: If PACT is to be used in environmental applications, the matrix containing target microbial communities should be previously characterized in order to establish an efficient protocol having into account the photosensitizer concentration, the light source and the total light dose delivered. The possibility of using solar light in PACT to treat aquaculture water makes this technology cost-effective and attractive.

A new protocol for the preparation of thioaryl-porphyrins is described. The compounds were prepared from different disulfides employing NaBH4 as a reducing agent. The methodology allowed the preparation of four different thioaryl-porphyrins in very-good to excellent yields under soft conditions, such as short reaction times and smooth heating. Additionally, the photophysical properties of new compounds were determined and experimental and theoretical DNA interactions were assessed.

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 (10 7 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-CO 2 Me 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.

Porphyrins show great promise for future purification demands. This is largely due to their unique features as host binding molecules that can be modified at the synthetic level, and largely improved by their incorporation into inorganic based materials. In this study, we assessed the efficacy of a hybrid material obtained from the immobilization of 5,10,15,20-tetrakis(pentafluorophenyl)-porphyrin on silica surface to remove Pb(II), Cu(II), Cd(II), and Zn(II) ions from water. The new organic-inorganic hybrid adsorbent was fully characterized by adequate techniques and the results show that the hybrid exhibits good chemical and thermal stability. From batch assays, it was evaluated how the efficacy of the hybrid was affected by the pH, contact time, initial metal concentration, and temperature. The adsorption kinetic and isotherms showed to fit the recent developed fractal-like pseudo-second-order model and Langmuir–Freundlich model respectively. The highest adsorption capacities for Pb(II), Cu(II), Cd(II), and Zn(II) ions were 187.36, 125.17, 82.45, and 56.23 mg g−1, respectively, at pH 6.0 and 25 °C. This study also shows that metal cations from real river water samples can be efficient removed in the presence of the new adsorbent material.

We compare the semiclassical and quantum predictions for the unitary dynamics of a two-level atom interacting with a single-mode electromagnetic field under parametric modulation of the atomic parameters in the regime of multiphoton atom–field resonances. We derive approximate analytic solutions for the semiclassical Rabi model when the atomic transition frequency and the atom–field coupling strength undergo harmonic external modulations. These solutions are compared to the predictions of the quantum Rabi model, which we solve numerically for an initial coherent state with a large average photon number (on the order of 104), in the regime of three-photon resonance. We show that, for short enough times and sufficiently intense coherent states, the semiclassical dynamics agrees quite well with the quantum dynamics, although it inevitably fails at longer times due to the absence of collapse–revival behavior. Furthermore, we describe how the field state evolves throughout the interaction, presenting numerical results for the average photon number, entropies (related to atom–field entanglement), and other quantities characterizing the photon number statistics of the electromagnetic field.

Photodynamic action has been used for diverse biomedical applications, such as treating a broad range of bacterial infections. Based on the combination of light, dioxygen, and photosensitizer (PS), the photodynamic inactivation (PDI) approach led to the formation of reactive oxygen species (ROS) and represented a non-invasive, non-toxic, repeatable procedure for pathogen photoinactivation. To this end, different tetrapyrrolic macrocycles, such as porphyrin (Por) dyes, have been used as PSs for PDI against microorganisms, mainly bacteria. Still, there is significant room for improvement, especially new PS molecules. Herein, unsymmetrical new pyridinone (3–5) and thiopyridyl Pors (7) were prepared with α-, β-, or γ-cyclodextrin (CD) units, following their quaternization to perform the corresponding free-base Pors (3a–5a and 7a), and were compared with the already-known Pors 6a and 8a, both bearing thiopyridinium and CD units. These water-soluble porphyrins were evaluated as PSs, and their photophysical and photochemical properties and photodynamic effects on E. coli were assessed. The presence of one CD unit and three positive charges on the Por structure (3a–5a and 7a) enhanced their aqueous solubility. The photoactivity of the cationic Pors 3a–5a and 6a–8a ensured their potential against the Gram-negative bacterium E. coli. Within each series of methoxypyridinium vs thiopyridinium dyes, the best PDI efficiency was achieved for 5a with a bacterial viability reduction of 3.5 log10 (50 mW cm−2, 60 min of light irradiation) and for 8a with a total bacterial viability reduction (>8 log10, 25 mW cm−2, 30 min of light irradiation). Here, the presence of the methoxypyridinium units is less effective against E. coli when compared with the thiopyridinium moieties. This study allows for the conclusion that the peripheral charge position, quaternized substituent type/CD unit, and affinity to the outer bacterial structures play an important role in the photoinactivation efficiency of E. coli, evidencing that these features should be further addressed in the pursuit for optimised PS for the antimicrobial PDI of pathogenic microorganisms.