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.

The surfaces of electrospun polystyrene (PS) nanofiber materials with encapsulated 1% w/w 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were modified through sulfonation, radio frequency (RF) oxygen plasma treatment, and polydopamine coating. The nanofiber materials exhibited efficient photogeneration of singlet oxygen. The postprocessing modifications strongly increased the wettability of the pristine hydrophobic PS nanofibers without causing damage to the nanofibers, leakage of the photosensitizer, or any substantial change in the oxygen permeability of the inner bulk of the polymer nanofiber. The increase in the surface wettability yielded a significant increase in the photo-oxidation of external polar substrates and in the antibacterial activity of the nanofibers in aqueous surroundings. The results reveal the crucial role played by surface hydrophilicity/wettability in achieving the efficient photo-oxidation of a chemical substrate/biological target at the surface of a material generating O2((1)Δg) with a short diffusion length.

A simple nanoprecipitation method was used for preparation of stable photoactive polystyrene nanoparticles (NPs, diameter 30 ± 10 nm) from sulfonated electrospun polystyrene nanofiber membranes with encapsulated 5,10,15,20-tetraphenylporphyrin (TPP) or platinum octaethylporphyrin (Pt-OEP). The NPs prepared with TPP have strong antibacterial and antiviral properties and can be applied to the photooxidation of external substrates based on photogenerated singlet oxygen. In contrast to nanofiber membranes, which have limited photooxidation ability near the surface, NPs are able to travel toward target species/structures. NPs with Pt-OEP were used for oxygen sensing in aqueous media, and they presented strong linear responses to a broad range of oxygen concentrations. The nanofiber membranes can be applied not only as a source of NPs but also as an effective filter for their removal from solution.

We report the synthesis and characterization of sulfonated polystyrene nanoparticles (average diameter 30 ± 14 nm) with encapsulated 5,10,15,20-tetraphenylporphyrin or ionically entangled tetracationic 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin, their photooxidation properties, and the application of singlet oxygen-sensitized delayed fluorescence (SODF) in oxygen sensing. Both types of nanoparticles effectively photogenerated singlet oxygen, O(Δ). The O(Δ) phosphorescence, transient absorption of the porphyrin triplet states, and SODF signals were monitored using time-resolved spectroscopic techniques. The SODF intensity depended on the concentration of the porphyrin photosensitizer and dissolved oxygen and on the temperature. After an initial period (a few microseconds), the kinetics of the SODF process can be approximated as a monoexponential function, and the apparent SODF lifetimes can be correlated with the oxygen concentration. The oxygen sensing based on SODF allowed measurement of the dissolved oxygen in aqueous media in the broad range of oxygen concentrations (0.2-38 mg L). The ability of both types of nanoparticles to photooxidize external substrates was predicted by the SODF measurements and proven by chemical tests. The relative photooxidation efficacy was highest at a low porphyrin concentration, as indicated by the highest fluorescence quantum yield (Φ), and it corresponds with negligible inner filter and self-quenching effects. The photooxidation abilities were sensitive to the influence of temperature on the diffusion and solubility of oxygen in both polystyrene and water media and to the rate constant of the O(Δ) reaction with a substrate. Due to their efficient photogeneration of cytotoxic O(Δ) at physiological temperatures and their oxygen sensing via SODF, both types of nanoparticles are promising candidates for biomedical applications.

This contribution reports on the preparation, characterization, and biological evaluation of electrospun polystyrene nanofiber materials engineered with a covalently grafted NO photodonor and ionically entangled tetracationic porphyrin and phthalocyanine photosensitizers. These photofunctional materials exhibit an effective and simultaneous photogeneration of two antibacterial species such as nitric oxide (NO) and singlet oxygen, O2((1)Δg) under illumination with visible light, as demonstrated by their direct detection using amperometric and time-resolved spectroscopic techniques. Dual-mode photoantibacterial action is demonstrated by antibacterial tests carried out on Escherichia coli.