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Subject: computer simulations ×

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    Stacks of Azobenzene Stars: Self-Assembly Scenario and Stabilising Forces Quantified in Computer Modelling
    (Basel : MDPI, 2019) Savchenko, Vladyslav; Koch, Markus; Pavlov, Aleksander S.; Saphiannikova, Marina; Guskova, Olga
    In this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analyzed theoretically by applying a combination of computer simulation techniques. Without a light stimulus, the azobenzene arms adopt the trans-state and build one-dimensional columns of stacked molecules during the first stage of the noncovalent association. These columnar aggregates represent the structural elements of more complex experimentally observed morphologies-fibers, spheres, gels, and others. Here, we determine the most favorable mutual orientations of the trans-stars in the stack in terms of (i) the p - p distance between the cores lengthwise the aggregate, (ii) the lateral displacements due to slippage and (iii) the rotation promoting the helical twist and chirality of the aggregate. To this end, we calculate the binding energy diagrams using density functional theory. The model predictions are further compared with available experimental data. The intermolecular forces responsible for the stability of the stacks in crystals are quantified using Hirshfeld surface analysis. Finally, to characterize the self-assembly mechanism of the stars in solution, we calculate the hydrogen bond lengths, the normalized dipole moments and the binding energies as functions of the columnar length. For this, molecular dynamics trajectories are analyzed. Finally, we conclude about the cooperative nature of the self-assembly of star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core in aqueous solution.
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    Tailoring the Cavity of Hollow Polyelectrolyte Microgels
    (Weinheim : Wiley-VCH, 2020) Wypysek, Sarah K.; Scotti, Andrea; Alziyadi, Mohammed O.; Potemkin, Igor I.; Denton, Alan R.; Richtering, Walter
    The authors demonstrate how the size and structure of the cavity of hollow charged microgels may be controlled by varying pH and ionic strength. Hollow charged microgels based on N-isopropylacrylamide with ionizable co-monomers (itaconic acid) combine advanced structure with enhanced responsiveness to external stimuli. Structural advantages accrue from the increased surface area provided by the extra internal surface. Extreme sensitivity to pH and ionic strength due to ionizable moieties in the polymer network differentiates these soft colloidal particles from their uncharged counterparts, which sustain a hollow structure only at cross-link densities sufficiently high that stimuli sensitivity is reduced. Using small-angle neutron and light scattering, increased swelling of the network in the charged state accompanied by an expanded internal cavity is observed. Upon addition of salt, the external fuzziness of the microgel surface diminishes while the internal fuzziness grows. These structural changes are interpreted via Poisson–Boltzmann theory in the cell model. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.