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.
Polymeric polyurethane nanofabrics doped by zinc tetraphenylporphyrin (ZnTPP) and/or zinc phthalocyanine (ZnPc) photosensitizers were prepared by the electrospinning method and characterized by microscopic methods, steady-state and time-resolved fluorescence, and absorption spectroscopy. Nanofabrics doped by both ZnTPP and ZnPc efficiently harvest visible light to generate triplet states and singlet oxygen O2(1Delta(g)) with a lifetime of about 15 micros in air atmosphere. The energy transfer between the excited singlet states of ZnTPP and ground states of ZnPc is described in details. All nanofabrics have bactericidal surfaces and photooxidize inorganic and organic substrates. ZnTPP and ZnPc in the polyurethane nanofabrics are less photostable than incorporated free-base tetraphenylporphyrin (TPP).
2,5-Dimethylphenacyl (DMP) carbamates (1a-c) released the corresponding free amines or amino acids in high chemical yields, albeit with quantum yields Phi of only 0.04-0.09, upon irradiation in either aprotic or protic solvents. The photoreaction proceeded principally from the triplet excited state via the E-photoenol. The lifetimes of the triplet enol and the E- and Z-enols in the ground state were determined by laser flash photolysis. The primary photoinitiated transformation liberated a carbamic acid derivative, which subsequently decarboxylated to the amino group-containing compound. Exhaustive irradiation of a DMP-protected aniline (1a) in acetonitrile did not provide aniline in quantitative chemical yields, because it was involved in reductive cleavage of the starting material as an electron donor, thereby decreasing the overall deprotection yield (86%). Phenylalanine methyl ester, liberated from 1c, was, however, obtained in excellent chemical yield (97%). It was also found that the carbamates, while thermally stable, released amines with higher quantum yields in acidic methanol solutions. The DMP chromophore is proposed as an excellent photoremovable protecting group for amino acids and, under specific conditions, for amines in organic synthesis and biochemistry.
Novel biomaterials based on hydrophilic polycaprolactone and polyurethane (Tecophilic®) nanofibers with an encapsulated 5,10,5,20-tetraphenylporphyrin photosensitizer were prepared by electrospinning. The doped nanofiber textiles efficiently photo-generate O2(1Δg), which oxidize external chemical and biological substrates/targets. Strong photo-virucidal effects toward non-enveloped polyomaviruses and enveloped baculoviruses were observed on the surface of these textiles. The photo-virucidal effect was confirmed by a decrease in virus infectivity. In contrast, no virucidal effect was detected in the absence of light and/or the encapsulated photosensitizer.
Anion exchange polystyrene nanofiber materials (AE) were prepared by electrospinning followed by two-step functionalization of the nanofiber surface by chlorosulfonic acid and ethylendiamine. The photoactive character of these materials was introduced through adsorption of the tetra-anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin photosensitizer (TPPS-AE) on the nanofiber surface or by encapsulation of the nonpolar 5,10,15,20-tetraphenylporphyrin photosensitizer (AE(TPP)) into the nanofibers. Anion exchange nanofiber materials with porphyrins are characterized by a high ion-exchange capacity, photogeneration of singlet oxygen O2((1)Δg), and singlet oxygen-sensitized delayed fluorescence. Due to the photogeneration of cytotoxic O2((1)Δg), the nanofibers exhibited oxidation of the external substrates in aqueous solution and an efficient antibacterial effect when activated by simulated daylight. Adsorption of both TPPS and I(-) on the surface of AE led to the formation of more efficient I-TPPS-AE materials. Rapid photooxidation of I(-) by O2((1)Δg), and the formation of another cytotoxic species, I3(-), on the surface of the nanofibers were responsible for the increased antibacterial properties of I-TPPS-AE and the prolonged antibacterial effect in the dark.
Irradiation of 2-(alkoxymethyl)-5-methyl-alpha-chloroacetophenones (1a-c) and 2-(methoxymethyl)-5-methylphenacyl benzoate (1d) in dry, nonnucleophilic solvents afforded 3-alkoxy-6-methylindan-1-ones (3a-c) in very high chemical yields. 3-Methylisobenzofuran-1(3H)-one (2) was, however, isolated as a major photoproduct in the presence of trace amounts of water. Quenching experiments and laser flash spectroscopy revealed that the indanone derivatives 3 are formed by 1,5-hydrogen migration from the lowest triplet excited state of the acetophenones 1 and cyclization of the resulting photoenols. In contrast, production of the lactone 2 in wet solvents was found to result from two consecutive photochemical transformations. The photoenols produced by photolysis of 1a-c add water as a nucleophile to form 2-acetyl-4-methylbenzaldehyde (4), which is further converted to 2 via a second, singlet state photoenolization process. Exhaustive photolysis of 1a in methanol produced the acetal 2-(dimethoxymethyl)-5-methylacetophenone (7a) as the exclusive product. The remarkable selectivity of these photoreactions may well be useful in synthetic organic chemistry.
The aim was to construct a composite structure for bone tissue substitute on the basis of a degradable composite of an organic nanofiber carrier and an inorganic matrix in 3D, and to achieve subsequent colonisation by differentiated human mesenchymal stem cells (hMSC) towards osteocytes. We developed an active bone tissue substitute using nanofiber technology for a polycaprolactone (PCL) scaffold with the addition of hydroxyapatite and the colonisation of both components with hMSC with the ability of differentiation towards osteocytes. The constructed composition included the components necessary for bone healing (inorganic and cellular) and it also forms a spatially-oriented 3D structure. We used polycaprolactone Mw 70,000 with electrostatic spinning for the formation of nanofibers using a modified Nanospider TM method. For the inorganic component we used orthophosphate-calcium silicate with a crystal size of 1-2 mm which the nanofiber membrane was coated with. Both components were connected together with a tissue adhesive based of fibrin glue. Cultivated hMSC cells at a concentration of 1.2 × 10 4 /cm 2 were multiplied in vitro and then cultivated in the expansion medium. HMSC overgrew both the PCL membrane and the Si-CaP crystals. After colonisation with cultivated cells, this composite 3D structure can serve as a three-dimensional bone tissue replacement.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.