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Register a new userSoft Interaction Between Dissolved Dendrimers: Theory and Experiment
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Using small-angle neutron scattering and liquid integral equation theory, we relate the structure factor of flexible dendrimers of 4th generation to their average shape. The shape is measured as a radial density profile of monomers belonging to a single dendrimer. From that, we derive an effective interaction of Gaussian form between pairs of dendrimers and compute the structure factor using the hypernetted chain approximation. Excellent agreement with the corresponding experimental results is obtained, without the use of adjustable parameters. The present analysis thus strongly supports the previous finding that flexible dendrimers of low generation present fluctuating structures akin to star polymers.
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We study the influence of mutual interaction on the conformation of flexible poly(propyleneamine) dendrimers of fourth generation in concentrated solution. Mixtures of dendrimers with protonated and deuterated end groups are investigated by small-angle neutron scattering up to volume fractions of 0.23. This value is in the range of the overlap concentration of the dendrimers. The contrast between the solute and the solvent was varied by using mixtures of protonated and deuterated solvents. This allows us to investigate the partial structure factors of the deuterated dendrimers in detail. An analysis of the measured scattering intensities reveals that the shape of the flexible dendrimers is practically independent of the concentration in contrast to the pronounced conformational changes of flexible linear polymers.
We study the average separation between an elastic solid and a hard solid with a nominal flat but randomly rough surface, as a function of the squeezing pressure. We present experimental results for a silicon rubber (PDMS) block with a flat surface squeezed against an asphalt road surface. The theory shows that an effective repulse pressure act between the surfaces of the form p proportional to exp(-u/u0), where u is the average separation between the surfaces and u0 a constant of order the root-mean-square roughness, in good agreement with the experimental results.
In this study we consider an idealization of a typical optical tweezers experiment involving a semiflexible double-knotted polymer, with steric hindrance and persistence length matching those of dsDNA in high salt concentration, under strong stretching. Using exhaustive Molecular Dynamics simulations we show that not only does a double-knotted dsDNA filament under tension possess a free energy minimum when the two knots are intertwined, but also that the depth of this minimum depends on the relative chirality of the two knots. We rationalize this dependence of the effective interaction on the chirality in terms of a competition between chain entropy and bending energy.
Compact and extended dendrimers are two important classes of dendritic polymers. The impact of the underlying structure of compact dendrimers on dynamical processes has been much studied, yet the relation between the dynamical and structural properties of extended dendrimers remains not well understood. In this paper, we study the trapping problem in extended dendrimers with generation-dependent segment lengths, which is different from that of compact dendrimers where the length of the linear segments is fixed. We first consider a particular case that the deep trap is located at the central node, and derive an exact formula for the average trapping time (ATT) defined as the average of the source-to-trap mean first passage time over all starting points. Then, using the obtained result we deduce a closed-form expression for the ATT to an arbitrary trap node, based on which we further obtain an explicit solution to the ATT corresponding to the trapping issue with the trap uniformly distributed in the polymer systems. We show that the trap location has a substantial influence on the trapping efficiency measured by the ATT, which increases with the shortest distance from the trap to the central node, a phenomenon similar to that for compact dendrimers. In contrast to this resemblance, the leading terms of ATTs for the three trapping problems differ drastically between extended and compact dendrimers, with the trapping processes in the extended dendrimers being less efficient than in compact dendrimers.
By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $sim f^{1/4}$ and the effective interaction as $sim f^{2}$, as opposed to $sim f^{1/5}$ and $sim f^{3/2}$, respectively, in three dimensions. Our results demonstrate the dramatic effect that geometric confinement can have on the effective interactions and the subsequent correlations of soft colloids in general, for which the conformation can be altered as a result of geometrical constraints imposed on them.
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