Frozen State of Sephadex® Gels of Different Crosslink Density Analyzed by X-ray Computed Tomography and X-ray Diffraction.

Water in Sephadex® (crosslinked dextran) gels is known to indicate different freezing behavior which is dependent on the density of the crosslinks, and water in a Sephadex® G25 gel remains partially unfrozen during cooling and crystallizes during rewarming. The mechanism of anomalous ice crystallization during rewarming is still unclear. The objective of this study is to observe the ice grains that form in Sephadex® beads and to comprehend their frozen state with a focus on the ice crystallization during rewarming. Sephadex® beads containing 50 wt % water were prepared and used for the measurements. The observation of the ice grains was carried out by using synchrotron radiation-sourced X-ray CT (computed tomography). XRD (X-ray diffraction) analysis was also conducted to investigate the frozen state. As a result, ice grains that were larger than ~1 µm were hardly observed after the slow cooling of Sephadex® beads, except in the G25 beads. However, at the occurrence of ice crystallization during rewarming, ice grains that were larger than 10 µm appeared in the G25 beads. Using XRD, it was found that small incomplete ice crystals were formed in G25 beads and the presence of glassy water was indicated in the gel. In conclusion, the size and distribution of ice grains that formed in Sephadex® beads were different depending on the density of the crosslinks.

Photophysical properties of a carbazolyl mesogen of 8PCzC as revealed by absorption, fluorescence, and transient absorption measurements.

Fluorescence spectra in three phases [crystalline, smectic A liquid crystal (SmA), and isotropic] of a mesogen including one carbazolyl (Cz) chromophore, 4'-n-octylphenyl carbazole-2-carboxylate (8PCzC), were measured at various temperatures and compared with fluorescence spectra in solvents with various dielectric constants. Further, for the first time, picosecond transient absorption spectroscopy was applied to elucidating photoinduced electron-transfer dynamics (charge separation, charge recombination, and hole transfer reactions) in the three phases of 8PCzC doped with a small amount of an electron acceptor. The fluorescence spectra showed clearly the presence of two crystalline phases, which was supported by DSC measurement. On the basis of a comparison of the fluorescence spectra and those in solution, the 8PCzC molecule in the first crystal structure was suggested to be in polar environment compared to that in the second one. The fluorescence yields of 8PCzC in both SmA and isotropic phases were remarkably small compared to that in crystalline one. This was ascribed to the formation of hydrogen bonds between 8PCzC molecules in both SmA and isotropic phases. As a first approximation, the picosecond transient absorption spectra in the three phases of 8PCzC doped with 2,4,7-trinitrofluorenone were analyzed by the simple model of one-dimensional hole migration. The rate constants obtained for the hole transfer from the cation state of Cz chromophore to neighboring Czs decreased in the order of SmA (approximately 10(9) s(-1)) > isotropic (approximately 10(8) s(-1)) > crystalline (approximately 10(7) s(-1)) phases, although these measurement temperatures were different.