Bulk dynamics of Brownian hard disks: Dynamical density functional theory versus experiments on two-dimensional colloidal hard spheres

Using dynamical density functional theory (DDFT), we theoretically study Brownian self-diffusion and structural relaxation of hard disks and compare to experimental results on quasi two-dimensional colloidal hard spheres. To this end, we calculate the self and distinct van Hove correlation functions by extending a recently proposed DDFT-approach for three-dimensional systems to two dimensions. We find that the theoretical results for both self- and distinct part of the van Hove function are in very good quantitative agreement with the experiments up to relatively high fluid packing fractions of roughly 0.60. However, at even higher densities, deviations between experiment and the theoretical approach become clearly visible. Upon increasing packing fraction, in experiments the short-time self diffusive behavior is strongly affected by hydrodynamic effects and leads to a significant decrease in the respective mean-squared displacement. In contrast, and in accordance with previous simulation studies, the present DDFT which neglects hydrodynamic effects, shows no dependence on the particle density for this quantity

3D Flow Field Measurements Outside Nanopores

We demonstrate a non-stereoscopic, video-based particle tracking system with optical tweezers to study fluid flow in 3D in the vicinity of glass nanopores. In particular, we used the Quadrant Interpolation algorithm to extend our video-based particle tracking to displacements out of the trapping plane of the tweezers. This permitted the study of flow from nanopores oriented at an angle to the trapping plane, enabling the mounting of nanopores on a micromanipulator with which it was then possible to automate the mapping procedure. Mapping of voltage driven flow in 3D volumes outside nanopores revealed polarity dependent flow fields. This is in agreement with the model of voltage driven flow in conical nanopores depending on the interaction of distinct flows within the nanopore and along the outer walls.Comment: 3 pages, 3 figure

Direct detection of molecular intermediates from first-passage times

All natural phenomena are governed by energy landscapes. However, the direct measurement of this fundamen-tal quantity remains challenging, particularly in complex systems involving intermediate states. Here, we uncover key details of the energy landscapes that underpin a range of experimental systems through quantitative analysis of first-passage time distributions. By combined study of colloidal dynamics in confinement, transport through a biological pore, and the folding kinetics of DNA hairpins, we demonstrate conclusively how a short-time, power-law regime of the first-passage time distribution reflects the number of intermediate states associated with each of these processes, despite their differing length scales, time scales, and interactions. We thereby establish a powerful method for investigating the underlying mechanisms of complex molecular processes

Tunable Anion-Selective Transport through Monolayer Graphene and Hexagonal Boron Nitride.

Membranes that selectively filter for both anions and cations are central to technological applications from clean energy generation to desalination devices. 2D materials have immense potential as these ion-selective membranes due to their thinness, mechanical strength, and tunable surface chemistry; however, currently, only cation-selective membranes have been reported. Here we demonstrate the controllable cation and anion selectivity of both monolayer graphene and hexagonal boron nitride. In particular, we measure the ionic current through membranes grown by chemical vapor deposition containing well-known defects inherent to scalably produced and wet-transferred 2D materials. We observe a striking change from cation selectivity with monovalent ions to anion selectivity by controlling the concentration of multivalent ions and inducing charge inversion on the 2D membrane. Furthermore, we find good agreement between our experimental data and theoretical predictions from the Goldman-Hodgkin-Katz equation and use this model to extract selectivity ratios. These tunable selective membranes conduct up to 500 anions for each cation and thus show potential for osmotic power generation

The eukaryotic CO2-concentrating organelle is liquid-like and exhibits dynamic reorganization

Approximately 30%–40% of global CO 2 fixation occurs inside a non-membrane-bound organelle called the pyrenoid, which is found within the chloroplasts of most eukaryotic algae. The pyrenoid matrix is densely packed with the CO 2-fixing enzyme Rubisco and is thought to be a crystalline or amorphous solid. Here, we show that the pyrenoid matrix of the unicellular alga Chlamydomonas reinhardtii is not crystalline but behaves as a liquid that dissolves and condenses during cell division. Furthermore, we show that new pyrenoids are formed both by fission and de novo assembly. Our modeling predicts the existence of a “magic number” effect associated with special, highly stable heterocomplexes that influences phase separation in liquid-like organelles. This view of the pyrenoid matrix as a phase-separated compartment provides a paradigm for understanding its structure, biogenesis, and regulation. More broadly, our findings expand our understanding of the principles that govern the architecture and inheritance of liquid-like organelles

Children's understanding of mixed emotions

Understanding mixed emotions is important for various aspects of functioning and evidence suggests that mixed emotion understanding improves with development. Research has suggested that this understanding might proceed differently in anxious children, however there has been little research conducted in this area to date. An initial exploration investigating mixed emotion understanding was conducted with children aged between 7 and 12 years that were experiencing anxiety concerns. This provided initial evidence for the appropriateness of a story-based psychoeducation technique for enhancing mixed emotions in anxious children: it was found to be highly engaging and was considered by children to be helpful and enjoyable. Mixed emotion understanding is a task that can pose a challenge for all children, particularly when the emotions occur in children's family relationships. This thesis therefore also investigated the development of mixed emotion understanding in typically developing children aged between 6 and 12 years in the context of mother-child relationships. Results showed that younger children demonstrated less understanding than older children, that different combinations of emotions were understood equally well by children, and that children of all ages could provide diverse reasons for how mixed emotions can occur. However, only a minority of children reported mixed emotion experience in their own lives. Girls demonstrated greater mixed emotion understanding than boys, but only on more stringent tests of mixed emotion understanding. Most children felt that mixed emotions would be "mixed up" and disliked, and children reported a variety of coping methods for managing any discomfort associated with mixed emotions

Structure and dynamics of two-dimensional colloidal hard spheres

The structural and dynamic behaviour of quasi-two-dimensional monodisperse and bidisperse colloidal hard spheres are studied by optical microscopy. Firstly, a full characterisation of the equilibrium structure is presented through a consideration of structural correlation functions and number fluctuations. Comparison to fundamental measure theory and Monte Carlo simulations confirms both the behaviour of the system as a model for hard disks and the equation of state. The differing structural behaviour of binary systems at different size ratios is also discussed in relation to the nonadditivity. Next, the short- and long-time self-diffusion of particles is considered. Results for the long-time diffusion coefficient are again compared to Monte Carlo simulations, which demonstrates that at long times the dynamic behaviour is effectively not affected by hydrodynamic interactions. Additionally, simple theoretical expressions for the area fraction dependence of the short- and long-time diffusion coefficients are discussed. The selfdynamic properties of particles are probed further using the self-intermediate scattering function and the self-van Hove correlation function. In particular, the extent to which these quantities may be described by the Gaussian approximation is considered in relation to the relevant hydrodynamic limits for colloidal systems. A scaling relation to describe the crossover between these limits at short and long times is also developed. The consideration of dynamic behaviour is then extended to collective phenomena and, in particular, to the process of interdiffusion. Here, the thermodynamic and kinetic drives for this process are explored for binary systems at two different size ratios. The differing interdiffusive effects seen in the two systems are considered in light of the predictions of the Darken equation. Finally, the melting of quasi-two-dimensional colloidal hard spheres is studied by considering a monolayer of particles in sedimentation-diffusion equilibrium. Density profiles and the equation of state are used to characterise the system. These quantities display a discontinuity, indicating a coexistence gap and hence an interface. This interface is located and analysed using capillary wave theory, from which both the size of the coexistence gap and the anisotropic stiffness of the interface are determined.</p

Structure and dynamics of two-dimensional colloidal hard spheres

The structural and dynamic behaviour of quasi-two-dimensional monodisperse and bidisperse colloidal hard spheres are studied by optical microscopy. Firstly, a full characterisation of the equilibrium structure is presented through a consideration of structural correlation functions and number fluctuations. Comparison to fundamental measure theory and Monte Carlo simulations confirms both the behaviour of the system as a model for hard disks and the equation of state. The differing structural behaviour of binary systems at different size ratios is also discussed in relation to the nonadditivity. Next, the short- and long-time self-diffusion of particles is considered. Results for the long-time diffusion coefficient are again compared to Monte Carlo simulations, which demonstrates that at long times the dynamic behaviour is effectively not affected by hydrodynamic interactions. Additionally, simple theoretical expressions for the area fraction dependence of the short- and long-time diffusion coefficients are discussed. The selfdynamic properties of particles are probed further using the self-intermediate scattering function and the self-van Hove correlation function. In particular, the extent to which these quantities may be described by the Gaussian approximation is considered in relation to the relevant hydrodynamic limits for colloidal systems. A scaling relation to describe the crossover between these limits at short and long times is also developed. The consideration of dynamic behaviour is then extended to collective phenomena and, in particular, to the process of interdiffusion. Here, the thermodynamic and kinetic drives for this process are explored for binary systems at two different size ratios. The differing interdiffusive effects seen in the two systems are considered in light of the predictions of the Darken equation. Finally, the melting of quasi-two-dimensional colloidal hard spheres is studied by considering a monolayer of particles in sedimentation-diffusion equilibrium. Density profiles and the equation of state are used to characterise the system. These quantities display a discontinuity, indicating a coexistence gap and hence an interface. This interface is located and analysed using capillary wave theory, from which both the size of the coexistence gap and the anisotropic stiffness of the interface are determined.</p