Segmental dynamics of polymer by rotational fluorescence correlation microscopy.

The segmental dynamics of polymers is known to be closely related to the glass transition where the glass transition is the single most important parameter in its application. In this study, we designed an efficient and reliable experimental method to study the ensemble segmental dynamics of polymers by probing rotation of fluorescent molecules in the polymer matrix using a home-built microscope setup. The rotational dynamics of fluorescent molecules was analyzed using a fluorescence correlation method that extracts information through orthogonally polarized fluorescence images. From fluorescence intensities, autocorrelation functions (ACFs) were obtained in many areas simultaneously and by averaging several ACFs, well-defined ACF and precise experimental values were obtained from a single measurement movie. The robustness of the method and optimal experimental conditions were investigated by performing experiments with various probe concentrations, frame rates, and measurement lengths. By employing a home-built vacuum chamber, a wide temperature range was achieved, and we demonstrate the versatility and efficiency of imaging rotational FCM (fluorescence correlation microscopy) by probing segmental dynamics of different polymeric systems with glass transition temperature that differ by ≈100 K and with fragility ranging from 49 to 131. The imaging rotational FCM covers dynamics up to 4 orders of magnitude near the glass transition, and it was found that the rapidity of the stretching exponent ß variation with temperature correlates with the fragility of polymers.

Attenuating Fibrotic Markers of Patient-Derived Dermal Fibroblasts by Thiolated Lignin Composites.

We report the use of phenolic functional groups of lignosulfonate to impart antioxidant properties and the cell binding domains of gelatin to enhance cell adhesion for poly(ethylene glycol) (PEG)-based scaffolds. Chemoselective thiol-ene chemistry was utilized to form composites with thiolated lignosulfonate (TLS) and methacrylated fish gelatin (fGelMA). Antioxidant properties of TLS were not altered after thiolation and the levels of antioxidation were comparable to those of L-ascorbic acid. PEG-fGelMA-TLS composites significantly reduced the difference in COL1A1, ACTA2, TGFB1, and HIF1A genes between high-scarring and low-scarring hdFBs, providing the potential utility of TLS to attenuate fibrotic responses.

How Tethered Probes Report the Dynamics of a Polymer near the Glass Transition.

How tethered probes report dynamics of host polymers near the glass transition was investigated by changing the length of the flexible linkers and the number of tethering points via imaging rotational fluorescence correlation microscopy and compared with free probes of different sizes. The results show that tethering did not alter the temperature-dependence of polymer dynamics and the shape of the correlation decay reported by the probe; however, the rotation slowed down up to ≈1 decade when both ends of the probe were restricted with short alkyl chain linkers. Upon comparison with the bigger free probe, the mechanism of the slowdown was attributed to the restricted motion upon tethering for tethered probes compared to averaging over different regions of the dynamic heterogeneity for the bigger probe. If the size of the probe was comparable to that of the dynamic heterogeneity of the system, tethered probes accurately report dynamics relevant to glass transition, regardless of tethering conditions.