The deformation mechanism of “slide-ring” (SR) gels was investigated with small-angle neutron scattering (SANS). The SR gels were prepared by coupling α-cyclodextrin (CD) molecules on polyrotaxane chains consisting of poly(ethylene glycol) and CD. Because of a hollow structure of CD molecules, the cross-links made of CD molecules in a figure-of-eight shape can slide along the polymer chain. A normal butterfly pattern was observed for the first time in two-dimensional SANS isointensity profiles for the SR gels under uniaxial deformation, where the normal butterfly pattern means a prolate isointensity pattern in the direction perpendicular to the stretching direction. However, by either increasing the cross-link density or increasing the stretching ratio, the normal butterfly patterns changed to abnormal butterfly patterns as are commonly observed in conventional covalent-bonded chemical gels. The difference in the deformation mechanism as well as the cross-linking inhomogeneities between the SR gels and the covalent-bonded chemical gels is discussed by focusing on the unique architecture of the SR gels.
Rising temperatures caused by climate change could negatively alter plant ecosystems if temperatures exceed optimal temperatures for carbon gain. Such changes may threaten temperature‐sensitive species, causing local extinctions and range migrations. This study examined the optimal temperature of net photosynthesis (Topt) of two boreal and four temperate deciduous tree species grown in the field in northern Minnesota, United States under two contrasting temperature regimes. We hypothesized that Topt would be higher in temperate than co‐occurring boreal species, with temperate species exhibiting greater plasticity in Topt, resulting in better acclimation to elevated temperatures. The chamberless experiment, located at two sites in both open and understory conditions, continuously warmed plants and soils during three growing seasons. Results show a modest, but significant shift in Topt of 1.1 ± 0.21 °C on average for plants subjected to a mean 2.9 ± 0.01 °C warming during midday hours in summer, and shifts with warming were unrelated to species native ranges. The 1.1 °C shift in Topt with 2.9 °C warming might be interpreted as suggesting limited capacity to shift temperature response functions to better match changes in temperature. However, Topt of warmed plants was as well‐matched with prior midday temperatures as Topt of plants in the ambient treatment, and Topt in both treatments was at a level where realized photosynthesis was within 90–95% of maximum. These results suggest that seedlings of all species were close to optimizing photosynthetic temperature responses, and equally so in both temperature treatments. Our study suggests that temperate and boreal species have considerable capacity to match their photosynthetic temperature response functions to prevailing growing season temperatures that occur today and to those that will likely occur in the coming decades under climate change.
Thermoreversible gelation and microphase formation of aqueous solutions of a methylated polyrotaxane (MePR) were investigated by means of differential scanning microcalorimetry, rheometry, and X-ray diffractometry (XRD). The aqueous solutions of MePR show a lower critical solution temperature (LCST) and form an elastic gel with increasing temperature. The sol-gel transition of the MePR solutions was induced by formation and deformation of aggregates of methylated alpha-cyclodextrins (alpha-CDs) of polyrotaxane due to hydrophobic dehydration and hydration, respectively. The XRD investigation revealed localization and highly ordered arrangement of methylated alpha-CDs along the PEG chain in the gel. The arrangement of CDs was also reflected by the changes in elasticity and long relaxation behavior of the solution around the sol-gel transition. The quasiequilibrium shear modulus of MePR solutions showed the critical phenomena against temperature. The scaling exponents measured at two different concentrations were almost equal to the values predicted by a gel percolation theory. Therefore, the heat-induced gelation of aqueous MePR solutions is well explained by a model in which clusters assembled with methylated alpha-CDs are gradually connected to the network as the temperature increases.
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