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Subject: Molecules × WGL Institute: IPF ×

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Now showing 1 - 3 of 3
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    Entropy driven chain effects on ligation chemistry
    (Cambridge : RSC, 2014) Pahnke, Kai; Brandt, Josef; Gryn'ova, Ganna; Lindner, Peter; Schweins, Ralf; Schmidt, Friedrich Georg; Lederer, Albena; Coote, Michelle L.; Barner-Kowollik, Christopher
    We report the investigation of fundamental entropic chain effects that enable the tuning of modular ligation chemistry – for example dynamic Diels–Alder (DA) reactions in materials applications – not only classically via the chemistry of the applied reaction sites, but also via the physical and steric properties of the molecules that are being joined. Having a substantial impact on the reaction equilibrium of the reversible ligation chemistry, these effects are important when transferring reactions from small molecule studies to larger or other entropically very dissimilar systems. The effects on the DA equilibrium and thus the temperature dependent degree of debonding (%debond) of different cyclopentadienyl (di-)functional poly(meth-)acrylate backbones (poly(methyl methacrylate), poly(iso-butyl methacrylate), poly(tert-butyl methacrylate), poly(iso-butyl acrylate), poly(n-butyl acrylate), poly(tert-butyl acrylate), poly(methyl acrylate) and poly(isobornyl acrylate)), linked via a difunctional cyanodithioester (CDTE) were examined via high temperature (HT) NMR spectroscopy as well as temperature dependent (TD) SEC measurements. A significant impact of not only chain mass and length with a difference in the degree of debonding of up to 30% for different lengths of macromonomers of the same polymer type but – remarkably – as well the chain stiffness with a difference in bonding degrees of nearly 20% for isomeric poly(butyl acrylates) is found. The results were predicted, reproduced and interpreted via quantum chemical calculations, leading to a better understanding of the underlying entropic principles.
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    Structure and Bottom-up Formation Mechanism of Multisheet Silica-Based Nanoparticles Formed in an Epoxy Matrix through an In Situ Process
    (Washington, DC : ACS Publ., 2021) Branda, Francesco; Bifulco, Aurelio; Jehnichen, Dieter; Parida, Dambarudhar; Pauer, Robin; Passaro, Jessica; Gaan, Sabyasachi; Pospiech, Doris; Durante, Massimo
    Organic/inorganic hybrid composite materials with the dispersed phases in sizes down to a few tens of nanometers raised very great interest. In this paper, it is shown that silica/epoxy nanocomposites with a silica content of 6 wt % may be obtained with an “in situ” sol–gel procedure starting from two precursors: tetraethyl orthosilicate (TEOS) and 3-aminopropyl-triethoxysilane (APTES). APTES also played the role of a coupling agent. The use of advanced techniques (bright-field high-resolution transmission electron microscopy, HRTEM, and combined small- and wide-angle X-ray scattering (SAXS/WAXS) performed by means of a multirange device Ganesha 300 XL+) allowed us to evidence a multisheet structure of the nanoparticles instead of the gel one typically obtained through a sol–gel route. A mechanism combining in a new manner well-assessed knowledge regarding sol–gel chemistry, emulsion formation, and Ostwald ripening allowed us to give an explanation for the formation of the observed lamellar nanoparticles.
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    STM induced manipulation of azulene-based molecules and nanostructures: the role of the dipole moment
    (Cambridge : RSC Publ., 2020) Kühne, Tim; Au-Yeung, Kwan Ho; Eisenhut, Frank; Aiboudi, Oumaima; Ryndyk, Dmitry A.; Cuniberti, Gianaurelio; Lissel, Franziska; Moresco, Francesca
    Among the different mechanisms that can be used to drive a molecule on a surface by the tip of a scanning tunneling microscope at low temperature, we used voltage pulses to move azulene-based single molecules and nanostructures on Au(111). Upon evaporation, the molecules partially cleave and form metallo-organic dimers while single molecules are very scarce, as confirmed by simulations. By applying voltage pulses to the different structures under similar conditions, we observe that only one type of dimer can be controllably driven on the surface, which has the lowest dipole moment of all investigated structures. Experiments under different bias and tip height conditions reveal that the electric field is the main driving force of the directed motion. We discuss the different observed structures and their movement properties with respect to their dipole moment and charge distribution on the surface.