Effect of Chain Stiffness on the Structure of Single-Chain Polymer Nanoparticles

Polymeric single-chain nanoparticles (SCNPs) are soft nano-objects synthesized by purely intramolecular cross-linking of single polymer chains. By means of computer simulations, we investigate the conformational properties of SCNPs as a function of the bending stiffness of their linear polymer precursors. We investigate a broad range of characteristic ratios from the fully flexible case to those typical of bulky synthetic polymers. Increasing stiffness hinders bonding of groups separated by short contour distances and increases looping over longer distances, leading to more compact nanoparticles with a structure of highly interconnected loops. This feature is reflected in a crossover in the scaling behaviour of several structural observables. The scaling exponents change from those characteristic for Gaussian chains or rings in $\theta$-solvents in the fully flexible limit, to values resembling fractal or `crumpled' globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs.Comment: 20 pages, 17 figure

Mapping the “Extra Solvent Power, ESP” of Ionic Liquids for Monomers, Polymers and Globular Nanoparticles

Understanding the miscibility behavior of ionic liquid (IL) / monomer, IL / polymer and IL / nanoparticle mixtures is critical for the use of ILs as green solvents in polymerization processes, and to rationalize recent observations concerning the superior solubility of some proteins in ILs when compared to standard solvents. In this work, the most relevant results obtained in terms of a three-component Flory-Huggins theory concerning the “Extra Solvent Power, ESP” of ILs when compared to traditional non-ionic solvents for monomeric solutes (case I), linear polymers (case II) and globular nanoparticles (case III) are presented. Moreover, useful ESP maps are drawn for the first time for IL mixtures corresponding to case I, II and III. Finally, a potential pathway to improve the miscibility of non-ionic polymers in ILs is also proposed

Electrical characterization of new electrochromic devices

Electrochromic devices change their color and optical properties with applied voltage. A new symmetrical electrochromic configuration was constructed in previous works, where PEDOT acted as electrochromic layer or as counter electrode layer, depending on the polarity of the applied voltage. Devices of around 500mm2 and switching voltages from 0,5V to 2V are used in this work. Measured electrochemical impedance is fitted to an equivalent circuit based on a Randles cell, with Warburg impedance simulating ionic diffusion at low frequencies. Voltage dependence is analyzed for the first time in this kind of devices. Results show homogeneity problems in the contact layers, not seen in normal operation, and the voltage dependence on some construction parameters. This will be used to improve the devices construction, but improvements in the equivalent circuit should also be made. The proposed equivalent circuit is not valid after the redox reaction, from 1.5 to 2V.<br /