Polydiacetylenes (PDAs) are conjugative polymers that demonstrate color changes as a response to an external stimulus. In this study, 10,12-pentacosadiynoic acid (PCDA) was mixed with a supporting polymer including poly(ethylene oxide) (PEO) and polyurethane (PU), and the mixture solution was electrospun to construct fiber composites. The electrospun fibers were then photopolymerized using UV irradiation to produce PEO–PDA and PU–PDA nanofiber mats with a fiber diameter ranging from 130 nm to 2.5 μm. The morphologies of both PEO–PDA and PU–PDA nanofibers were dependent on electrospinning parameters such as the ratio of PCDA to PEO or PCDA to PU and the total polymer concentrations. Scanning electron microscopy images showed beaded fibers of PEO–PDA and PU–PDA at 2 and 18 w/v % concentrations, respectively. Smooth fibers were found when the solvent concentration was increased to 3.75 w/v % in PEO–PDA and 25 w/v % in PU–PDA fibers. Both PEO–PDA and PU–PDA nanofiber composites demonstrated excellent colorimetric responses to the presence of Escherichia coli ATCC25922 bacterial cells and the changes in pH as external stimuli. The nanofibers underwent a rapid colorimetric response when exposed directly to E. coli ATCC25922 grown on Luria–Bertani agar. The comparison between the PEO–PDA and PU–PDA suggested that the combination of PEO and PDA is favorable because it provides a sensitive response to the presence of E. coli. The results were compared with samples of a PDA polymer in the absence of a matrix polymer. The colorimetric response was similar when the PDA polymer and the PDA nanofiber composites were exposed to pH changes, and the color change was found to occur at pH 10 and enhanced at pH 11–13. The PDA-containing nanofiber composites showed stronger colorimetric responses than those of the PDA polymer only, suggesting their potential as biosensors and chemosensors.
Polydiacetylene (PDA) is an attractive conjugated material for use in biosensors due to its unique characteristic of undergoing a blue-to-red color change in response to external stimuli. 10,12-Pentacosadiynoic acid (PCDA) and poly (ethylene oxide) (PEO) were used in this study to develop fiber composites via an electrospinning method at various mass ratios of PEO to PCDA, solution concentrations, and injection speeds. The PEO-PDA fibers in blue phase were obtained via photo-polymerization upon UV-light irritation. High mass ratios of PEO to PCDA, low polymer concentrations of spinning solution, and low injection speeds promoted fine fibers with small diameters and smooth surfaces. The colorimetric transition of the fibers was investigated when the fibers were heated at temperatures ranging from 25 °C to 120 °C. A color switch from blue to red in the fibers was observed when the fibers were heated at temperatures greater than 60 °C. The color transition was more sensitive in the fibers made with a low mass ratio of PEO to PCDA due to high fraction of PDA in the fibers. The large diameter fibers also promoted the color switch due to high reflectance area in the fibers. All of the fibers were analyzed using Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) and compared before and after the color change occurred. The colorimetric transitional mechanism is proposed to occur due to conformational changes in the PDA macromolecules.
Herein, we report the synthesis and characterization of biodegradable citrate-based polyesters that were functionalized for nitric oxide release. The material extracts did not exhibit cytotoxicity as evaluated with human dermal fibroblasts.
S-Nitrosoglutathione (GSNO) is a naturally available S-nitrosothiol that can be incorporated into non-toxic formulations intended for topical use. The value of nitric oxide (NO) delivered topically relates to its wellstudied physiological functions such as vasodilation, angiogenesis, cell proliferation and broad-spectrum antibacterial activity. Previously reported topical NO-releasing substrates include polymeric materials that exhibit non-toxic behaviors on dermal tissue such as polyethylene glycol. However, they do not serve as humectants nor provide vitamins to the skin. In this study, GSNO was added to an emulsion that was fortified with a-tocopheryl acetate (vitamin E) and hyaluronic acid. The average total NO content for the NO-releasing emulsion was 58 AE 8 mmol g À1 at 150 C and the cumulative NO release over 53 h at physiological temperature (37.4 C) was 46 AE 4 mmol g À1 . The GSNO concentration in the lotion was optimized in order to reach a pH value similar to that of human skin (pH 5.5). The viscosity was analyzed using a rotational viscometer for the S-nitrosated and the non-nitrosated emulsions to obtain a material that can be readily spread on dermal tissue. The viscosity values obtained ranged from 7.88 AE 0.99 to 8.50 AE 0.36 Pa s. Previous studies have determined that the viscosity maximum for lotions is 100 Pa s. A low viscosity increases the diffusion coefficient of active ingredients to the skin given that they are inversely proportional as described by the Einstein-Smoluchowski equation. The effect of the Snitrosated and non-nitrosated emulsions on adult human dermal fibroblasts (HDFs) was assessed in comparison to untreated HDFs using Colorimetric Cell Viability Kit I-WST-8. The findings indicate that neither the S-nitrosated nor non-nitrosated emulsions induced cytotoxicity in HDFs. † Electronic supplementary information (ESI) available: Nitric oxide release proles using a chemiluminescence-based detection method are shown (n ¼ 3). See
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