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    Polymerization driven monomer passage through monolayer chemical vapour deposition graphene
    ([London] : Nature Publishing Group UK, 2018-10-3) Zhang, Tao; Liao, Zhongquan; Sandonas, Leonardo Medrano; Dianat, Arezoo; Liu, Xiaoling; Xiao, Peng; Amin, Ihsan; Gutierrez, Rafael; Chen, Tao; Zschech, Ehrenfried; Cuniberti, Gianaurelio; Jordan, Rainer
    Mass transport through graphene is receiving increasing attention due to the potential for molecular sieving. Experimental studies are mostly limited to the translocation of protons, ions, and water molecules, and results for larger molecules through graphene are rare. Here, we perform controlled radical polymerization with surface-anchored self-assembled initiator monolayer in a monomer solution with single-layer graphene separating the initiator from the monomer. We demonstrate that neutral monomers are able to pass through the graphene (via native defects) and increase the graphene defects ratio (Raman ID/IG) from ca. 0.09 to 0.22. The translocations of anionic and cationic monomers through graphene are significantly slower due to chemical interactions of monomers with the graphene defects. Interestingly, if micropatterned initiator-monolayers are used, the translocations of anionic monomers apparently cut the graphene sheet into congruent microscopic structures. The varied interactions between monomers and graphene defects are further investigated by quantum molecular dynamics simulations.
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    Distinguishing autocrine and paracrine signals in hematopoietic stem cell culture using a biofunctional microcavity platform
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Müller, Eike; Wang, Weijia; Qiao, Wenlian; Bornhäuser, Martin; Zandstra, Peter W.; Werner, Carsten; Pompe, Tilo
    Homeostasis of hematopoietic stem cells (HSC) in the mammalian bone marrow stem cell niche is regulated by signals of the local microenvironment. Besides juxtacrine, endocrine and metabolic cues, paracrine and autocrine signals are involved in controlling quiescence, proliferation and differentiation of HSC with strong implications on expansion and differentiation ex vivo as well as in vivo transplantation. Towards this aim, a cell culture analysis on a polymer microcavity carrier platform was combined with a partial least square analysis of a mechanistic model of cell proliferation. We could demonstrate the discrimination of specific autocrine and paracrine signals from soluble factors as stimulating and inhibitory effectors in hematopoietic stem and progenitor cell culture. From that we hypothesize autocrine signals to be predominantly involved in maintaining the quiescent state of HSC in single-cell niches and advocate our analysis platform as an unprecedented option for untangling convoluted signaling mechanisms in complex cell systems being it of juxtacrine, paracrine or autocrine origin.
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    Universal size ratios of Gaussian polymers with complex architecture: radius of gyration vs hydrodynamic radius
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2020) Haydukivska, Khristine; Blavatska, Viktoria; Paturej, Jarosław
    We study the impact of arm architecture of polymers with a single branch point on their structure in solvents. Many physical properties of polymer liquids strongly dependent on the size and shape measures of individual macromolecules, which in turn are determined by their topology. Here, we use combination of analytical theory, based on path integration method, and molecular dynamics simulations to study structural properties of complex Gaussian polymers containing fc linear branches and fr closed loops grafted to the central core. We determine size measures such as the gyration radius Rg and the hydrodynamic radii RH, and obtain the estimates for the size ratio Rg/RH with its dependence on the functionality f=fc+fr of grafted polymers. In particular, we obtain the quantitative estimate of the degree of compactification of these polymers with increasing number of closed loops fr as compared to linear or star-shape molecules of the same total molecular weight. Numerical simulations corroborate theoretical prediction that Rg/RH decreases towards unity with increasing f. These findings provide qualitative description of polymers with complex architecture in θ solvents.