Porous protoporphyrin IX-embedded cellulose diacetate electrospun microfibers in antimicrobial photodynamic inactivation.

Motivated by the need for self-disinfecting materials that can be used to reduce the surface transmission of harmful microbes to healthy hosts, here we prepared a photodynamic antimicrobial membrane comprised of electrospun cellulose diacetate (CA) microfibers into which the photosensitizer protoporphyrin IX (PpIX) was in situ embedded. The resultant porous PpIX-embedded CA (PpIX/CA) microfibrous membranes were prepared with two different photosensitizer loadings: 5 and 10 wt% PpIX with respect to CA (85 and 170 nmol PpIX/mg membrane, respectively). The singlet oxygen (1O2) generated by the embedded photosensitizer was confirmed by electron paramagnetic resonance spectroscopic studies through generation of the TEMPO radical, and its photooxidation efficiency was further investigated using potassium iodide as a model substrate. Antibacterial photodynamic inactivation studies showed that the PpIX/CA membrane achieved a 99.8% reduction in Gram-positive S. aureus after illumination (Xe lamp, 65 ± 5 mW/cm2, λ ≥ 420 nm; 30 min), with a lower level of reduction (86.6%) for Gram-negative E. coli. Potentiation with potassium iodide was found to be an effective way to further enhance the antimicrobial efficacy of the PpIX/CA microfibrous membrane, achieving 99.9999% (6 log units) inactivation of both S. aureus and E. coli in the presence of 25 and 100 mM KI, respectively. These findings indicate that the electrospun CA microfibrous membrane is an ideal matrix for a photosensitizer such as PpIX to be embedded and effectively sensitized upon visible light illumination, and its antimicrobial photodynamic inactivation efficiency could be strongly enhanced with the increased KI addition, showing a promising future for its use in pathogen transmission defensive materials.

Color-Variable Photodynamic Antimicrobial Wool/Acrylic Blended Fabrics.

Towards the goal of developing scalable, economical and effective antimicrobial textiles to reduce infection transmission, here we prepared color-variable photodynamic materials comprised of photosensitizer (PS)-loaded wool/acrylic (W/A) blends. Wool fibers in the W/A blended fabrics were loaded with the photosensitizer rose bengal (RB), and the acrylic fibers were dyed with a variety of traditional cationic dyes (cationic yellow, cationic blue and cationic red) to broaden their color range. Investigations on the colorimetric and photodynamic properties of a series of these materials were implemented through CIELab evaluation, as well as photooxidation and antibacterial studies. Generally, the photodynamic efficacy of these dual-dyed fabrics was impacted by both the choice, and how much of the traditional cationic dye was employed in the dyeing of the W/A fabrics. When compared with the PS-only singly-dyed material, RB-W/A, that showed a 99.97% (3.5 log units; p = 0.02) reduction of Staphylococcus aureus under visible light illumination (λ ≥ 420 nm, 60 min), the addition of cationic dyes led to a slight decrease in the photoinactivation ability of the dual-dyed fabrics, but was still able to achieve a 99.3% inactivation of S. aureus. Overall, our findings demonstrate the feasibility and potential applications of low cost and color variable RB-loaded W/A blended fabrics as effective self-disinfecting textiles against pathogen transmission.

Carbon quantum dots: A bright future as photosensitizers for in vitro antibacterial photodynamic inactivation.

Carbon nanomaterials have increasingly gained the attention of the nano-, photo- and biomedical communities owing to their unique photophysical properties. Here, we facilely synthesized carbon quantum dots (CQDs) in a one-pot solvothermal reaction, and demonstrated their utility as photosensitizers for in vitro antibacterial photodynamic inactivation (aPDI). The bottom-up synthesis employed inexpensive and sustainable starting materials (citric acid), used ethanol as an environmentally-friendly solvent, was relatively energy efficient, produced minimal waste, and purification was accomplished simply by filtration. The CQDs were characterized by both physical (TEM, X-ray diffraction) and spectroscopic (UV-visible, fluorescence, and ATR-FTIR) methods, which together confirmed their nanoscale dimensions and photophysical properties. aPDI studies demonstrated detection limit inactivation (99.9999 + %) of Gram-negative Escherichia coli 8099 and Gram-positive Staphylococcus aureus ATCC-6538 upon visible light illumination (λ ≥ 420 nm, 65 ± 5 mW/cm2; 60 min). Post-illumination SEM images of the bacteria incubated with the CQDs showed perforated and fragmented cell membranes consistent with damage from reactive oxygen species (ROS), and mechanistic studies revealed that the bacteria were inactivated by singlet oxygen, with no discernable roles for other ROS (e.g., superoxide or hydroxyl radicals). These findings demonstrated that CQDs can be facilely prepared, operate via a Type II mechanism, and are effective photosensitizers for in vitro aPDI.

TiO2 Sol-Gel Coated PAN/O-MMT Multi-Functional Composite Nanofibrous Membrane Used as the Support for Laccase Immobilization: Synergistic Effect between the Membrane Support and Enzyme for Dye Degradation.

Removal of a triphenylmethane dye (crystal violet, CV) by a simultaneous enzymatic-photocatalytic-adsorption treatment was investigated in this work. A desirable synergistic effect on dye treatment was achieved by decorating laccase (Lac) onto the surface of TiO2 sol-gel coated polyacrylonitrile/organically modified montmorillonite (PAN/O-MMT) nanofibers prepared by electrospinning. The assembly of Lac on the surface of PAN/O-MMT/TiO2 nanofibers was confirmed by confocal laser scanning microscope (CLSM). In comparison with free Lac, the immobilized Lac showed better pH, temperature and operational stabilities, reaching highest relative activity at an optimum pH of 3 and optimum temperature of 50 °C. Therefore, the immobilized Lac displayed a higher degradation efficiency of CV at an initial dye concentration of 100 mg/L, an optimum pH of 4.5 and temperature at 60 °C. Under UV illumination, the CV removal efficiency was further improved by ~20%. These results demonstrated that the Lac-immobilized PAN/O-MMT/TiO2 composite nanofibers with a combined effect between the immobilized enzyme and the polymeric support have potential for industrial dye degradation.