Deriving GENERIC from a Generalized Fluctuation Symmetry

Much of the structure of macroscopic evolution equations for relaxation to equilibrium can be derived from symmetries in the dynamical fluctuations around the most typical trajectory. For example, detailed balance as expressed in terms of the Lagrangian for the path-space action leads to gradient zero-cost flow. We expose a new such fluctuation symmetry that implies GENERIC, an extension of gradient flow where a Hamiltonian part is added to the dissipative term in such a way as to retain the free energy as Lyapunov function.     

Death and Resurrection of a Current by Disorder,Interaction or Periodic Driving

We present several models of biased transport on (random) comb-like structures and on percolating backbones, that allow full mathematical control. We show how power-law corrections in the distribution of trap sizes may lead to a discontinuity in the current-field characteristic: the current jumps to zero when the driving exceeds a threshold. The current may resurrect when the field is modulated in time, also discontinuously: a little shaking enables the current to jump up. Finally, exclusion between particles postpones or even prevents the current from dying, while attraction such as modeled in zero range processes may expedite it.     

Thermo‐Responsive Solid‐Phase Extraction Using Poly(methyl vinyl ether)–Containing Segmented Polymer Networks

Segmented polymer networks containing poly(methyl vinyl ether) (PMVE) segments were prepared by free‐radical‐initiated copolymerization of PMVE‐α,ω‐dimethacrylate with styrene or 2‐hydroxyethyl methacrylate (HEMA). These networks were evaluated as thermo‐responsive solid‐phase extraction materials. Suspension‐derived polymer networks consisting of 80% of PMVE and 20% of HEMA adsorb toluene from an aqueous solution at 40°C and release the adsorbed toluene quantitatively at 20°C.     

2-Nitroimidazole Based PET Tracers: Development of a General Synthetic Approach and Fluorination Methodology

2-Nitroimidazole based PET tracers are widely used for non-invasive hypoxic tumor diagnosis. In this context, we report here a general method based on a central Mitsunobu reaction to easily access 2-nitroimidazole precursors. Optimization of fluorination conditions is described and successfully applied to the radiofluorination of the 2-nitroimidazole precursors. Moreover, the radiosynthesis of a new potential hypoxia PET tracer is also described. Finally, this article presents a SFC analytical method allowing both an easy monitoring of the fluorination reactions and the measurement of partition coefficients (logP).     

Polymer networks containing crystallizable poly(octadecyl vinyl ether) segments for shape‐memory materials

New polymer networks were prepared by free radical initiated copolymerization of crystallizable α,ω‐bismethacrylate‐terminated poly(octadecyl vinyl ether) (polyODVE) with butyl acrylate (BA). The polyODVE bismacromonomers were obtained by end‐capping the bifunctionally living cationic polymerization of ODVE with 2‐hydroxyethyl methacrylate (HEMA). The segmented networks show a high degree of phase separation over a wide range of compositions. The shape memory properties of a material containing 20 wt.‐% of polyODVE are reported.     

The sol-gel approach towards thermo-responsive poly(N-isopropyl acrylamide) hydrogels with improved mechanical properties

A new type of thermo-responsive hydrogels based on the polymer poly(N-isopropyl acrylamide) (PNIPAA) has been synthesized with the sol-gel technology. For the preparation of this type of nano-structured hydrogels, the inorganic silica phase was synthesized by the sol-gel process in the presence of an aqueous solution of high molecular weight PNIPAA. This combination of the organic and inorganic phases forms hybrid hydrogels with a semi-IPN morphology. The unique structure of these hydrogels improves the mechanical stability to a great extent as compared to conventional PNIPAA-hydrogels. This was shown by stress-strain experiments and the capability to absorb and desorb large amounts of water. The silica only slightly influences the transition temperature of the hydrogels but allows us to vary the thermo-responsive properties of the materials to a great extent.