We study the permeability and selectivity (`permselectivity') of model membranes made of polydisperse polymer networks for molecular penetrant transport, using coarse-grained, implicit-solvent computer simulations. In our work, the permeability P...

Replacing all protons on a polymer by deuterium has a dramatic impact on spin-dependent properties of the material in devices.

Certain species of living creatures are known to orientate themselves in the geomagnetic field. Given the small magnitude of approximately 48 µT, the underlying quantum mechanical phenomena are expected to exhibit coherence times approaching the millisecond regime. In this contribution, we show sensitivity of organic light-emitting diodes (OLEDs) to magnetic fields far below Earth's magnetic field, suggesting that coherence times of the spins of charge-carrier pairs in these devices can be similarly long. By electron paramagnetic resonance (EPR) experiments, a lower bound for the coherence time can be assessed directly. Moreover, this technique offers the possibility to determine the distribution of hyperfine fields within the organic semiconductor layer. We extend this technique to a material system exhibiting both fluorescence and phosphorescence, demonstrating stable anticorrelation between optically detected magnetic resonance (ODMR) spectra in the singlet (fluorescence) and triplet (phosphorescence) channel. The experiments demonstrate the extreme sensitivity of OLEDs to both static as well as dynamic magnetic fields and suggest that coherent spin precession processes of Coulombically bound electron spin pairs may play a crucial role in the magnetoreceptive ability of living creatures.

The selective solute partitioning within a polymeric network is of key importance to applications in which controlled release or uptake of solutes in a responsive hydrogel is required. In this work we investigate the impact of cross-links on solute adsorption in a swollen polymer network by means of all-atom, explicit-water molecular dynamics simulations. We focus on a representative network subunit consisting of poly(N -isopropylacrylamide) (PNIPAM) and N ,N -methylenebisacrylamide (BIS/MBA) cross-linker types. Our studied system consists of one BIS-linker with four atactic PNIPAM chains attached in a tetrahedral geometry. The adsorption of several representative solutes of different polarity in the low concentration limit at the linker region is examined. We subdivide the solute adsorption regions and distinguish between contributions stemming from polymer chains and cross-link parts. In comparison to a single polymer chain, we observe that the adsorption of the solutes to the cross-link region can significantly differ, with details depending on the specific compounds' size and polarity. In particular, for solutes that have already a relatively large affinity to PNIPAM chains the dense cross-link region (where many-body attractions are at play) amplifies the local adsorption by an order of magnitude. We also find that the cross-link region can serve as a seed for the aggregation of mutually attractive solutes at higher solute concentrations. Utilizing the microscopic adsorption coefficients in a mean-field model of an idealized macroscopic polymer network, we extrapolate these results to the global solute partitioning in a swollen hydrogel and predict that these adsorption features may lead to non-monotonic partition ratios as a function of the cross-link density.

We are concerned with the dynamical description of the motion of a stochastic micro-swimmer with constant speed and fluctuating orientation in the long time limit by adiabatic elimination of the orientational variable. Starting with the corresponding full set of Langevin equations, we eliminate the memory in the stochastic orientation and obtain a stochastic equation for the position alone in the overdamped limit. An equivalent procedure based on the Fokker-Planck equation is presented as well.

The formation of excitons in OLEDs is spin dependent and can be controlled by electron‐paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin‐1/2 Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π‐conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero‐field feature and local hyperfine fields. The zero‐field peak results from a quasistatic magnetic‐field effect of the RF radiation for periods comparable to the carrier‐pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero‐field peak, we suggest that this result may constitute a fundamental low‐field limit of magnetic resonance in carrier‐pair‐based systems. OLEDs offer an alternative solid‐state platform to investigate the radical‐pair mechanism of magnetic‐field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.

The amount of cross-linking in the design of polymer materials is a key parameter for the modification of numerous physical properties, importantly, the permeability to molecular solutes. We consider networks with a diamond-like architecture and different cross-link ratios, concurring with a wide range of the polymer volume fraction. We particularly focus on the effect and the competition of two independent component-specific solute–polymer interactions, i.e., we distinguish between chain-monomers and cross-linkers, which individually act on the solutes and are altered to cover attractive and repulsive regimes. For this purpose, we employ coarse-grained, Langevin computer simulations to study how the cross-link ratio of polymer networks controls the solute partitioning, diffusion, and permeability. We observe different qualitative behaviors as a function of the cross-link ratio and interaction strengths. The permeability can be tuned ranging over two orders of magnitude relative to the reference bulk permeability. Finally, we provide scaling theories for the partitioning and diffusion that explicitly account for the component-specific interactions as well as the cross-link ratio and the polymer volume fraction. These are in overall good agreement with the simulation results and grant insight into the underlying physics, rationalizing how the cross-link ratio can be exploited to tune the solute permeability of polymeric networks.

The formation of excitons in OLEDs is spin dependent and can be controlled by electron‐paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin‐1/2 Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π‐conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero‐field feature and local hyperfine fields. The zero‐field peak results from a quasistatic magnetic‐field effect of the RF radiation for periods comparable to the carrier‐pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero‐field peak, we suggest that this result may constitute a fundamental low‐field limit of magnetic resonance in carrier‐pair‐based systems. OLEDs offer an alternative solid‐state platform to investigate the radical‐pair mechanism of magnetic‐field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.