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A new Mo 6 cluster complex and its silica and polyurethane composites have been synthesized and characterized. These materials are highly luminescent with emission above 650 nm, produce singlet oxygen with high efficiency, are photostable, and can be excited up to 580 nm. These proper-[a] Institute of Inorganic Chemistry of the AS CR, v.v.i Husinec-Ř ež 1001, 25068 Ř ež,

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Polystyrene ion-exchange nanofiber materials with large surface areas and adsorption capacities were prepared by electrospinning followed by the sulfonation and adsorption of a cationic 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin (TMPyP) photosensitizer on the nanofiber surfaces. The morphology, structure, and photophysical properties of these nanofiber materials were characterized by microscopic methods and steady-state and time-resolved fluorescence and absorption spectroscopies. The externally bound TMPyP can be excited by visible light to form triplet states and singlet oxygen O2((1)Δg) and singlet oxygen-sensitized delayed fluorescence (SODF). The photophysical properties of the nanofibers were strongly dependent on the amount of bound TMPyP molecules and their organization on the nanofiber surfaces. The nanofibers demonstrated photooxidative activity toward inorganic and organic molecules and antibacterial activity against E. coli due to the sensitized formation of O2((1)Δg) that is an effective oxidation/cytotoxic agent. The nanofiber materials also adsorbed heavy metal cations (Pb(2+)) and removed them from the water environment.

Polyurethane (PUR) nanofabrics based on nanofibers of average diameters in the range of 250-110 nm with different meso-tetraphenylporphyrin (TPP) loading (0.01-5 wt %) were prepared by an electrospinning process. The oxygen quenching of excited states and singlet oxygen-sensitized delayed fluorescence (SODF) of TPP were studied at different oxygen pressures. We found that TPP in PUR matrix is present in monomeric state, and it is easily accessed by oxygen. Analysis of the kinetics of the TPP triplet, singlet oxygen, and SODF indicates that repopulation of TPP fluorescent state includes reaction of singlet oxygen with TPP triplets. The integrated SODF achieved more than 20% of the prompt fluorescence for nanofabric loaded with 5 wt % TPP. The dependence of SODF intensity on the TPP concentration in nanofibers is nearly quadratic.

Electrospun polymeric nanofiber materials doped with 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were prepared from four different polymers and were characterized with microscopic methods, steady-state, and time-resolved fluorescence and absorption spectroscopy. The polymers used included polyurethane Larithane™ (PUR), polystyrene (PS), polycaprolactone (PCL), and polyamide 6 (PA6). The antibacterial activity of all nanofiber materials against E. coli was activated by visible light and it was dependent on oxygen permeability/diffusion coefficients and the diameter of the polymeric nanofibers. This activity is based on oxidation ability of singlet oxygen O₂(¹Δ(g)) that is generated upon irradiation. All tested nanofiber materials exhibited prolonged antibacterial properties, even in the dark after long-duration irradiation. The post-irradiation effect was explained by the photogeneration of H₂O₂, which provided the material with long-lasting antibacterial properties.

This study presents new photofunctional materials producing singlet oxygen, 1O2, and investigates the interdependence between their structural and photophysical properties. These materials consist of Mg−Al layered double hydroxides (LDH) with intercalated photosensitizers, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) or Pd(II)-5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (PdTPPC). Powder X-ray diffraction and X-ray photoelectron spectroscopies were employed to characterize the host structure and confirm intercalation of porphyrins into the interlayer space. Because the kinetic parameters of the sensitizer triplet states predetermine the formation of 1O2, the excited-state kinetics of intercalated porphyrins were investigated by means of time-resolved diffuse reflectance. Comparison of the decay rates in the presence and absence of oxygen confirms that the triplet states of PdTPPC and TPPS in LDHs are quenched by oxygen. Photoproduction of 1O2 was monitored by time-resolved measurement of its luminescence at 1270 nm. It was established that PdTPPC-doped LDHs are very effective producers of 1O2, regardless of whether the porphyrin molecules are intercalated or adsorbed on the surface. The measured lifetimes of 1O2 lie in the 6−64 μs range, which means that the 1O2 molecules generated in the interior of LDHs can diffuse out of the matrix and react with a contiguous substrate. Dehydration of the LHD matrices enhances its singlet oxygen quenching capacity and inhibits the production of the long-lived 1O2 molecules, a process that can be reverted by exposing the material to atmospheric humidity. Consequently, we envisage LDHs with intercalated PdTPPC as efficient 1O2 sources whose oxidative activity can be modulated by successive dehydration−rehydration cycles.

The maintenance of an aseptic environment for chronic wounds is one of the most challenging tasks in the wound-healing process. Furthermore, the emergence of antibiotic-resistant bacterial strains is on the rise, rendering conventional treatments less effective. A new antibacterial material consisting of a polyurethane Tecophilic(™) nanofibre textile (NT) that was prepared by electrospinning and doped by a tetraphenylporphyrin (TPP) photosensitizer activated by visible light was tested for use in wound beds and bandages. In vitro experiments were performed to assess the antibacterial activity of the textile against three bacterial strains. Furthermore, the new textile was tested in 162 patients with chronic leg ulcers. A complete inhibition of in vitro growth of the three tested bacterial strains was observed on the surface of NTs that had been illuminated with visible light and was clinically demonstrated in 89 patients with leg ulcers. The application of the textiles resulted in a 35% decrease in wound size, as assessed via computer-aided wound tracing. Wound-related pain, which was estimated using a visual analogue scale, was reduced by 71%. The results of this trial reveal that the photoinactivation of bacteria through the photosensitized generation of short-lived, highly reactive singlet oxygen O(2) ((1) Δ(g) ) results in relatively superficial antibacterial effects in comparison with standard antiseptic treatment options. Thus, such treatment does not interfere with the normal healing process. This method therefore represents a suitable alternative to the use of topical antibiotics and antiseptics and demonstrates potentially broad applications in medicine.