Photophysical, photooxidation, and biomolecule-interaction of meso-tetra(thienyl)porphyrins containing peripheral Pt(II) and Pd(II) complexes. Insights for photodynamic therapy applications.

We report the synthesis and characterization of two novel tetra-cationic porphyrins, containing Pt(II) or Pd(II) polypyridyl complexes attached at the peripheral position of N4-macrocycle. Compounds were characterized through elemental analysis, molar conductivity, cyclic voltammetry, and spectroscopy analysis. Photophysical and photobiological parameters were also evaluated. Also, the binding capacity of each porphyrin with human serum albumin (HSA) was determined by UV-Vis, steady-state, and time-resolved fluorescence spectroscopy, combined with molecular docking calculations. The results suggest that the interaction of these compounds is spontaneous, weak to moderate, and probably occurs at site III (subdomain IB) by non-covalent forces, including van der Waals and H-bonding. Moreover, porphyrins containing peripheral complexes improve their interactions with biomolecules, show good photostability, generate reactive oxygen species under white light studied by electron paramagnetic resonance (EPR) analysis, and promote photo-damage of HSA.

Photodynamic therapy with a new bacteriochlorin derivative: Characterization and in vitro studies.

Photodynamic therapy presents a therapeutic choice that can be utilized to treat diverse neoplasms. In this technique, the critical element is a photosensitive molecule that absorbs light energy and transfers it to molecular oxygen or biological molecules to form reactive oxygen species, thus inducing irreversible damage to target cells and ultimately leading to cell death. Bacteriochlorin derivatives are employed as photosensitizers (PSs), possessing light-absorbing capacity in the near-infrared region. The objective of this study was to prepare a semi-synthetic bacteriochlorin from Rhodopseudomonas faecalis and adding Trizma® to improve solubility. Cell viability tests, flow cytometry (apoptotic and necrotic cells were identified by Annexin V and propidium iodide), and confocal microscopy were used to evaluate the photoactivity of bacteriochlorin-Trizma (Bchl-T) in fibroblast (HFF-1-control cells) and breast cancer (MCF-7 cells-target cells) cells. At concentrations above 0.5 µM, Bchl-T demonstrated 80 % cell death, presenting the highest PS interaction (via fluorescence microscopy) with lysosomes, mitochondria, and the endoplasmic reticulum; the cell death type was revealed as apoptosis (via cytometry). Our findings indicated the suitability of Bchl-T for future application in photodynamic therapy against cancer cells by inducing apoptosis.

Influence of light intensity and irradiation mode on methylene blue, chlorin-e6 and curcumin-mediated photodynamic therapy against Enterococcus faecalis.

This study aimed to evaluate the effect of the continuous irradiation with low intensity (continuous mode) and fractioned irradiation with high intensity (fractionated mode), keeping the same dose of light by using Light Emitting Diode (LEDs) with wavelength emission centered at 450 and at 660 nm, using methylene blue (MB), chlorin-e6 (Ce6) and curcumin (CUR) as photosensitizers (PSs) against planktonic phase of E. faecalis. Cell viability was assessed by counting colonies forming per mL (CFU/mL), and the quantification of reactive species was performed by fluorescence with the photodegradation rate evaluated by measurements of absorbance of PSs at different times. The results revealed that MB-mediated PDT was efficient to achieve total microbial load reduction in both irradiation modes, but in fractional mode it was possible to use a lower light dose. Using Ce6, a total bacterial reduction was observed when fractional light was used, but at the same light dose, there was no reduction in the continuous irradiation mode. CUR-mediated PDT under continuous irradiation mode promoted the total microbial load reduction. However, for fractional mode, a higher concentration of CUR was required to completely reduce E. faecalis cell viability. Our results suggest that the biological response to PDT is variable depending on the irradiation mode and on the photosensitizer. Therefore, these studies indicate that the irradiation mode, intensity and the specific PSs should be taken into account for the development of clinical protocols for PDT.

Photodynamic inactivation using a chlorin-based photosensitizer with blue or red-light irradiation against single-species biofilms related to periodontitis.

Chlorin-e6 (Ce6), as a photosensitizer (PS), has demonstrated significant reduction of microorganisms' viability when irradiated by red light. However, the main absorption peak of this PS is located at blue light spectrum, which is less investigated. This study aimed to evaluate the effect of pure-chlorin-e6-mediated photodynamic inactivation (PDI) using different light sources (450 or 660 nm) against biofilms related to periodontitis. Streptococcus oralis, Fusobacterium nucleatum, Porphyromonas gingivalis, and Aggregatibacter actinomycetemcomitans single-species biofilms were developed under proper conditions for five days. PDI was performed using different concentrations of Ce6 (100 and 200 mM), wavelengths (450 and 660 nm) and comparisons were made after colony forming unit and confocal laser scanning microscopy (CLSM) analysis. The use of light and PS were also individually tested. The greatest bacterial elimination was observed in the group where PDI was employed with blue light and concentration of 200 mM for all bacterial strains tested (4.01 log10 for A. actinomycetemcomitans, and total elimination for P. gingivalis and S. oralis), except for F. nucleatum, where 3.46 log10 reduction was observed when red light and 200 mM Ce6 were applied (p < 0.05). The antimicrobial effects of PDI mediated by Ce6 for all single pathogenic biofilms were confirmed by live/dead staining under CLSM analysis. For all single-species biofilms, the use of PDI mediated by chlorin-e6 photosensitizer under blue or red-light irradiation (450 and 660 nm) demonstrated a significant reduction in bacterial viability, but blue light showed a promising higher photobiological effect, encouraging its adjuvant use to basic periodontitis treatment.

Ion-exchange resin as a new tool for characterisation of coordination compounds and MOFs by NMR spectroscopy.

1H and 13C NMR spectroscopy is used to investigate the organic constituents of metal complexes, MOFs and coordination compounds synthesised under solvothermal and precipitation conditions. The elucidation of the ligands in paramagnetic compounds bearing Cu2+ (d9), Gd3+ (f7), Eu3+ (f6), Fe3+ (d5), ions after treatment with a cationic exchange resin is possible. We prove the efficiency of two post-synthesis linker modifications on diamagnetic IRMOF-3 Zn2+ (d10) with ethyl isocyanate and benzyl bromide.