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    Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers
    (Washington, DC : Soc., 2019) Mordvinkin, Anton; Suckow, Marcus; Böhme, Frank; Colby, Ralph H.; Creton, Costantino; Saalwächter, Kay
    We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate. © 2019 American Chemical Society.
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    The stress and vascular catastrophes in newborn rats: Mechanisms preceding and accompanying the brain hemorrhages
    (Lausanne : Frontiers Media, 2016) Semyachkina-Glushkovskaya, Oxana; Borisova, Ekaterina; Abakumov, Maxim; Gorin, Dmitry; Avramov, Latchezar; Fedosov, Ivan; Namykin, Anton; Abdurashitov, Arkady; Serov, Alexander; Pavlov, Alexey; Zinchenko, Ekaterina; Lychagov, Vlad; Navolokin, Nikita; Shirokov, Alexander; Maslyakova, Galina; Zhu, Dan; Luo, Qingming; Chekhonin, Vladimir; Tuchin, Valery; Kurths, Jürgen
    In this study, we analyzed the time-depended scenario of stress response cascade preceding and accompanying brain hemorrhages in newborn rats using an interdisciplinary approach based on: a morphological analysis of brain tissues, coherent-domain optical technologies for visualization of the cerebral blood flow, monitoring of the cerebral oxygenation and the deformability of red blood cells (RBCs). Using a model of stress-induced brain hemorrhages (sound stress, 120 dB, 370 Hz), we studied changes in neonatal brain 2, 4, 6, 8 h after stress (the pre-hemorrhage, latent period) and 24 h after stress (the post-hemorrhage period). We found that latent period of brain hemorrhages is accompanied by gradual pathological changes in systemic, metabolic, and cellular levels of stress. The incidence of brain hemorrhages is characterized by a progression of these changes and the irreversible cell death in the brain areas involved in higher mental functions. These processes are realized via a time-depended reduction of cerebral venous blood flow and oxygenation that was accompanied by an increase in RBCs deformability. The significant depletion of the molecular layer of the prefrontal cortex and the pyramidal neurons, which are crucial for associative learning and attention, is developed as a consequence of homeostasis imbalance. Thus, stress-induced processes preceding and accompanying brain hemorrhages in neonatal period contribute to serious injuries of the brain blood circulation, cerebral metabolic activity and structural elements of cognitive function. These results are an informative platform for further studies of mechanisms underlying stress-induced brain hemorrhages during the first days of life that will improve the future generation's health.