Enhancement of Electrocatalytic Oxygen Evolution by Chiral Molecular Functionalization of Hybrid 2D Electrodes

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes, to boost the oxygen evolution reaction (OER) by ca. 131.5% (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given.

Enhancement of Electrocatalytic Oxygen Evolution by Chiral Molecular Functionalization of Hybrid 2D Electrodes

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes, to boost the oxygen evolution reaction (OER) by ca. 131.5 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given.

Precise Measurements of the Temperature Influence on the Complex Permittivity of Power Transformers Moistened Paper-Oil Insulation

The reference characteristics of complex permittivity of the transformers insulation solid component were determined for use in the precise diagnostics of the power transformers insulation state. The solid component is a composite of cellulose, insulating oil and water nanoparticles. Measurements were made in the frequency range from 10−4 Hz to 5000 Hz at temperatures from 293.15 to 333.15 K. Uncertainty of temperature measurements was less than ±0.01 K. Pressboard impregnated with insulating oil with a water content of (5.0 ± 0.2) by weight moistened in a manner maximally similar to the moistening process in power transformers was investigated. It was found that there are two stages of changes in permittivity and imaginary permittivity components, occurring for low and high frequency. As the temperature increases, the frequency dependencies of the permittivity and imaginary permittivity component shifts to the higher frequency region. This phenomenon is related to the change of relaxation time with the increase in temperature. The values of relaxation time activation energies of the permittivity ΔWτε′ ≈ (0.827 ± 0.0094) eV and the imaginary permittivity component ΔWτε″ = 0.883 eV were determined. It was found that Cole-Cole charts for the first stage are asymmetric and similar to those described by the Dawidson–Cole relaxation. For stage two, the charts are arc-shaped, corresponding to the Cole-Cole relaxation. It has been established that in the moistened pressboard impregnated with insulating oil, there is an additional polarization mechanism associated with the occurrence of water in the form of nanodrops and the tunneling of electrons between them.

Active, Reactive, and Apparent Power in Dielectrophoresis: Force Corrections from the Capacitive Charging Work on Suspensions Described by Maxwell-Wagner’s Mixing Equation

A new expression for the dielectrophoresis (DEP) force is derived from the electrical work in a charge-cycle model that allows the field-free transition of a single object between the centers of two adjacent cubic volumes in an inhomogeneous field. The charging work for the capacities of the volumes is calculated in the absence and in the presence of the object using the external permittivity and Maxwell-Wagner’s mixing equation, respectively. The model provides additional terms for the Clausius-Mossotti factor, which vanish for the mathematical boundary transition toward zero volume fraction, but which can be interesting for narrow microfluidic systems. The comparison with the classical solution provides a new perspective on the notorious problem of electrostatic modeling of AC electrokinetic effects in lossy media and gives insight into the relationships between active, reactive, and apparent power in DEP force generation. DEP moves more highly polarizable media to locations with a higher field, making a DEP-related increase in the overall polarizability of suspensions intuitive. Calculations of the passage of single objects through a chain of cubic volumes show increased overall effective polarizability in the system for both positive and negative DEP. Therefore, it is proposed that DEP be considered a conditioned polarization mechanism, even if it is slow with respect to the field oscillation. The DEP-induced changes in permittivity and conductivity describe the increase in the overall energy dissipation in the DEP systems consistent with the law of maximum entropy production. Thermodynamics can help explain DEP accumulation of small objects below the limits of Brownian motion.

Magnetite/Poly(ortho-anisidine) Composite Particles and Their Electrorheological Response

Magnetic and semiconducting Fe3O4/poly(o-anisidine) (POA) core/shell composite particles were fabricated by an oxidation process using Fe3O4 synthesized separately. The dispersion stability in a liquid medium and the electrical conductivity of synthesized particles were improved because of the conductive POA polymeric shell. The morphological, microstructural, compositional/elemental, and thermal behaviors of the particles were characterized using SEM with energy dispersive X-ray spectroscopy, TEM, XRD, and thermogravimetric analysis, respectively. A smart electro-magneto-rheological suspension containing Fe3O4/POA particles with two functionalities, magnetism and conductivity, was prepared. Its electrorheological properties were investigated at different electric field strengths using a rotational rheometer. Without an electric field, the sample demonstrated typical Newtonian fluid behavior, as expected. However, while under the electric field, it exhibited a solid-like behavior, and the dynamic (or elastic) yield stress of the ER fluid increased linearly as a function of the electric field strength in a power-law function with an index of 2.0, following the polarization mechanism.

The role of vimentin-nuclear interactions in persistent cell motility through confined spaces

The ability of cells to move through small spaces depends on the mechanical properties of the cellular cytoskeleton and on nuclear deformability. In mammalian cells, the cytoskeleton is comprised of three interacting, semi-flexible polymer networks: actin, microtubules, and intermediate filaments (IF). Recent experiments of mouse embryonic fibroblasts with and without vimentin have shown that the IF vimentin plays a role in confined cell motility. We, therefore, develop a minimal model of cells moving through confined geometries that effectively includes all three types of cytoskeletal filaments with a cell consisting of an actomyosin cortex and a deformable cell nucleus and mechanical connections between the two cortices—the outer actomyosin one and the inner nuclear one. By decreasing the amount of vimentin, we find that the cell speed is typically faster for vimentin-null cells as compared to cells with vimentin. Vimentin-null cells also contain more deformed nuclei in confinement. Finally, vimentin affects nucleus positioning within the cell. By positing that as the nucleus position deviates further from the center of mass of the cell, microtubules become more oriented in a particular direction to enhance cell persistence or polarity, we show that vimentin-nulls are more persistent than vimentin-full cells. The enhanced persistence indicates that the vimentin-null cells are more subjugated by the confinement since their internal polarization mechanism that depends on cross-talk of the centrosome with the nucleus and other cytoskeletal connections is diminished. In other words, the vimentin-null cells rely more heavily on external cues. Our modeling results present a quantitative interpretation for recent experiments and have implications for understanding the role of vimentin in the epithelial-mesenchymal transition.

Programmed mechano-chemical coupling in reaction-diffusion active matter

Embryo morphogenesis involves a complex combination of pattern-forming mechanisms. However, classical in vitro patterning experiments explore only one mechanism at a time, thus missing coupling effects. Here, we conjugate two major pattern-forming mechanisms —reaction-diffusion and active matter— by integrating dissipative DNA/enzyme reaction networks within an active gel composed of cytoskeletal motors and filaments. We show that the strength of the flow generated by the active gel controls the mechano-chemical coupling between the two subsystems. We use this property to engineer the mechanical activation of chemical reaction networks both in time and space, thus mimicking key aspects of the polarization mechanism observed in C. elegans oocytes. We anticipate that reaction-diffusion active matter may be useful to investigate mechano-chemical transduction and to design new materials with life-like properties.