Pair interaction of localized topological structures in confined chiral media.

We study pairwise interactions between localized topological structures in chiral magnetic and cholesteric liquid crystal (CLC) systems confined in the planar geometry. Our calculations for magnetics are based on the lattice model that takes into account the bulk and surface anisotropies along with the exchange and the Dzyaloshinskii-Moriya interactions. In CLC cells, these anisotropies describe the energy of interaction with an external magnetic or electric field and the anchoring energy assuming that the magnetic or electric anisotropy is negative and the boundary conditions are homeotropic. We have selected the region of the phase diagram, where various localized solitonlike structures, including skyrmion tubes, torons, and leeches, embedded in the ground state of the z-cone (conical phase) coexist, and carried out numerical analysis of the distance dependencies of the effective intersoliton interaction potentials. For skyrmions and torons, the potentials are found to be attractive in the large separation region. It turned out that for these potentials, the effects of axial asymmetry are negligible. By contrast, it turned out that for the intermediate structures between the skyrmions and torons known as the leeches, the leech-leech potentials generally depend on the orientation of the intersoliton separation vector and their large distance parts may become repulsive at certain directions of the vector. All the potentials have the short distance repulsive parts and the local minima located at the equilibrium separations. It is found that the skyrmion-skyrmion potential has an additional metastable configuration shifted towards the short-distance region.

Confinement-Controlled Water Engenders Unusually High Electrochemical Capacitance.

The electrodynamics of nanoconfined water have been shown to change dramatically compared to bulk water, opening room for safe electrochemical systems. We demonstrate a nanofluidic "water-only" battery that exploits anomalously high electrolytic properties of pure water at firm confinement. The device consists of a membrane electrode assembly of carbon-based nanomaterials, forming continuously interconnected water-filled nanochannels between the separator and electrodes. The efficiency of the cell in the 1-100 nm pore size range shows a maximum energy density at 3 nm, challenging the region of the current metal-ion batteries. Our results establish the electrodynamic fundamentals of nanoconfined water and pave the way for low-cost and inherently safe energy storage solutions that are much needed in the renewable energy sector.

The Three-Phase Contact Potential Difference Modulates the Water Surface Charge.

The surface charge of an open water surface is crucial for solvation phenomena and interfacial processes in aqueous systems. However, the magnitude of the charge is controversial, and the physical mechanism of charging remains incompletely understood. Here we identify a previously overlooked physical mechanism determining the surface charge of water. Using accurate charge measurements of water microdrops, we demonstrate that the water surface charge originates from the electrostatic effects in the contact line vicinity of three phases, one of which is water. Our experiments, theory, and simulations provide evidence that a junction of two aqueous interfaces (e.g., liquid-solid and liquid-air) develops a pH-dependent contact potential difference Δϕ due to the longitudinal charge redistribution between two contacting interfaces. This universal static charging mechanism may have implications for the origin of electrical potentials in biological, nanofluidic, and electrochemical systems and helps to predict and control the surface charge of water in various experimental environments.

Speed of Evolution and Correlations in Multi-Mode Bosonic Systems.

We employ an exact solution of the thermal bath Lindblad master equation with the Liouvillian superoperator that takes into account both dynamic and environment-induced intermode couplings to study the speed of evolution and quantum speed limit (QSL) times of a open multi-mode bosonic system. The time-dependent QSL times are defined from quantum speed limits, giving upper bounds on the rate of change of two different measures of distinguishability: the fidelity of evolution and the Hilbert-Schmidt distance. For Gaussian states, we derive explicit expressions for the evolution speed and the QSL times. General analytical results are applied to the special case of a two-mode system where the intermode couplings can be characterized by two intermode coupling vectors: the frequency vector and the relaxation rate vector. For the system initially prepared in a two-mode squeezed state, dynamical regimes are generally determined by the intermode coupling vectors, the squeezing parameter and temperature. When the vectors are parallel, different regimes may be associated with the disentanglement time, which is found to be an increasing (a decreasing) function of the length of the relaxation vector when the squeezing parameter is below (above) its temperature-dependent critical value. Alternatively, we study dynamical regimes related to the long-time asymptotic behavior of the QSL times, which is characterized by linear time dependence with the proportionality coefficients defined as the long-time asymptotic ratios. These coefficients are evaluated as a function of the squeezing parameter at varying temperatures and relaxation vector lengths. We also discuss how the magnitude and orientation of the intermode coupling vectors influence the maximum speed of evolution and dynamics of the entropy and the mutual information.

Macroporous Silicone Chips for Decoding Microbial Dark Matter in Environmental Microbiomes.

Natural evolution has produced an almost infinite variety of microorganisms that can colonize almost any conceivable habitat. Since the vast majority of these microbial consortia are still unknown, there is a great need to elucidate this "microbial dark matter" (MDM) to enable exploitation in biotechnology. We report the fabrication and application of a novel device that integrates a matrix of macroporous elastomeric silicone foam (MESIF) into an easily fabricated and scalable chip design that can be used for decoding MDM in environmental microbiomes. Technical validation, performed with the model organism Escherichia coli expressing a fluorescent protein, showed that this low-cost, bioinert, and widely modifiable chip is rapidly colonized by microorganisms. The biological potential of the chip was then illustrated through targeted sampling and enrichment of microbiomes in a variety of habitats ranging from wet, turbulent moving bed biofilters and wastewater treatment plants to dry air-based environments. Sequencing analyses consistently showed that MESIF chips are not only suitable for sampling with high robustness but also that the material can be used to detect a broad cross section of microorganisms present in the habitat in a short time span of a few days. For example, results from the biofilter habitat showed efficient enrichment of microorganisms belonging to the enigmatic Candidate Phyla Radiation, which comprise ∼70% of the MDM. From dry air, the MESIF chip was able to enrich a variety of members of Actinobacteriota, which is known to produce specific secondary metabolites. Targeted sampling from a wastewater treatment plant where the herbicide glyphosate was added to the chip's reservoir resulted in enrichment of Cyanobacteria and Desulfobacteria, previously associated with glyphosate degradation. These initial case studies suggest that this chip is very well suited for the systematic study of MDM and opens opportunities for the cultivation of previously unculturable microorganisms.

Mechanism of ice nucleation in liquid water on alkali feldspars.

Crystallization of supercooled liquid water in most natural environments starts with heterogeneous nucleation of ice induced by a nucleation site. Mineral surfaces, which form the majority of aqueous interfaces in Earth's ecosystem, possess a plethora of surface morphological and chemical features that can serve as ice nucleation sites. The nature of surface sites responsible for ice nucleation from supersaturated water vapor have been recently identified for alkali feldspar, a family of rock-building minerals constituting 60% of the Earth's crust. It was demonstrated that ice preferentially forms upon the patches of crystalline surface with (100) orientation, exposed in the surface defects such as cracks, pores, and pits arising due to chemically induced stress and further enhanced by hydrothermal alterations of natural feldspars. However, whether the same sites were responsible for nucleation from liquid water, remained to be shown. Here, we investigate the mechanism of heterogeneous ice nucleation in a layer of aqueous sucrose solution on top of thin sections of feldspar prepared along the (010) crystalline plane. We observe a preferential orientation of ice crystals defined by an epitaxial relationship between feldspar and ice, with ice crystals growing on the crystalline surfaces of feldspar with (100) orientation. We thus conclude that the ice nucleating sites active in deposition freezing mode are also active in the immersion freezing regime. This conclusion is further supported by the enhancement of ice nucleation active site density observed for the thin sections of feldspar prepared sub-parallel to the (100) plane as compared to sections prepared along (010) and (001) crystallographic orientations.

Topological structures in chiral media: Effects of confined geometry.

We theoretically study orientational structures in chiral magnetics and cholesteric liquid crystal (CLC) nanosystems confined in the slab geometry. Our analysis is based on the model that, in addition to the exchange and the Dzyaloshinskii-Moriya interactions, takes into account the bulk and surface anisotropies. In CLC films, these anisotropies describe the energy of interaction with external magnetic/electric field and the anchoring energy assuming that magnetic/electric anisotropy is negative and the boundary conditions are homeotropic. We have computed the phase diagram and found that the ground state of the film is represented by various delocalized structures depending on the bulk and surface anisotropy parameters, κ^{b} and κ^{s}. These include the z helix and the z cone states, the oblique, and the x helicoids. The minimum energy paths connecting the ground state and metastable helicoids and the energy barriers separating these states are evaluated. We have shown that there is a variety of localized topological structures such as the skyrmion tube, the toron, and the bobber that can be embedded in different ground states including the z cone (conical phase) and tilted fingerprint states. We have also found the structure called the leech that can be viewed as an intermediate state between the toron and the skyrmion tube.

Lindblad Dynamics and Disentanglement in Multi-Mode Bosonic Systems.

In this paper, we consider the thermal bath Lindblad master equation to describe the quantum nonunitary dynamics of quantum states in a multi-mode bosonic system. For the two-mode bosonic system interacting with an environment, we analyse how both the coupling between the modes and the coupling with the environment characterised by the frequency and the relaxation rate vectors affect dynamics of the entanglement. We discuss how the revivals of entanglement can be induced by the dynamic coupling between the different modes. For the system, initially prepared in a two-mode squeezed state, we find the logarithmic negativity as defined by the magnitude and orientation of the frequency and the relaxation rate vectors. We show that, in the regime of finite-time disentanglement, reorientation of the relaxation rate vector may significantly increase the time of disentanglement.

Phase-only modulation of light.

We disclose the method to obtain polarization insensitive phase-only modulation that preserves both the state and the degree of polarization of light modulated using a medium with controlled birefringence. We find that, in the double-pass configuration involving reflection from the Faraday rotator mirror, such a medium acts as the phase-only modulator. The experimental data measured in the Michelson-interferometer-based setup for deformed-helix ferroelectric liquid crystal cells are found to be in good agreement with the theoretical results. For such cells, we experimentally demonstrate high-frequency (4 kHz modulation rate) 2π phase-only light modulation governed by the average phase shift and solve the problem of optical axes switching.

Multiple minimum-energy paths and scenarios of unwinding transitions in chiral nematic liquid crystals.

We apply the minimum-energy paths (MEPs) approach to study the helix unwinding transition in chiral nematic liquid crystals. A mechanism of the transition is determined by a MEP passing through a first order saddle point on the free energy surface. The energy difference between the saddle point and the initial state gives the energy barrier of the transition. Two starting approximations for the paths are used to find the MEPs representing different transition scenarios: (a) the director slippage approximation with in-plane helical structures and (b) the anchoring breaking approximation that involves the structures with profound out-of-plane director deviations. It is shown that, at sufficiently low voltages, the unwinding transition is solely governed by the director slippage mechanism with the planar saddle-point structures. When the applied voltage exceeds its critical value below the threshold of the Fréedericksz transition, the additional scenario through the anchoring breaking transitions is found to come into play. For these transitions, the saddle-point structure is characterized by out-of-plane deformations localized near the bounding surface. The energy barriers for different paths of transitions are computed as a function of the voltage and the anchoring energy strengths.

Direct catalytic arylation of heteroarenes with meso-bromophenyl-substituted porphyrins.

The arylation of mono-, di- and tetra-meso-bromophenyl-substituted porphyrins with the heteroarenes containing "acidic" C-H bonds, such as benzoxazole, benzothiazole and N-methylimidazole was studied in the presence of three alternative catalytic systems: Pd(dba)2/DavePhos/Cs2CO3, Pd(PPh3)4/PivOH/K2CO3 and Pd(OAc)2/Cu(OAc)2/PPh3/K2CO3. The first catalytic system was found to be successful in the reaction with benzoxazole, the second one was less efficient for our purpose, while the third system proved to be most versatile and afforded corresponding mono-, di-, tri- and even tetraarylated derivatives of porphyrins.

Modulation of unpolarized light in planar-aligned subwavelength-pitch deformed-helix ferroelectric liquid crystals.

We study the electro-optic properties of subwavelength-pitch deformed-helix ferroelectric liquid crystals (DHFLC) illuminated with unpolarized light. In the experimental setup based on the Mach-Zehnder interferometer, it was observed that the reference and the sample beams being both unpolarized produce the interference pattern which is insensitive to rotation of in-plane optical axes of the DHFLC cell. We find that the field-induced shift of the interference fringes can be described in terms of the electrically dependent Pancharatnam relative phase determined by the averaged phase shift, whereas the visibility of the fringes is solely dictated by the phase retardation.

Active sites in heterogeneous ice nucleation-the example of K-rich feldspars.

Ice formation on aerosol particles is a process of crucial importance to Earth's climate and the environmental sciences, but it is not understood at the molecular level. This is partly because the nature of active sites, local surface features where ice growth commences, is still unclear. Here we report direct electron-microscopic observations of deposition growth of aligned ice crystals on feldspar, an atmospherically important component of mineral dust. Our molecular-scale computer simulations indicate that this alignment arises from the preferential nucleation of prismatic crystal planes of ice on high-energy (100) surface planes of feldspar. The microscopic patches of (100) surface, exposed at surface defects such as steps, cracks, and cavities, are thought to be responsible for the high ice nucleation efficacy of potassium (K)-feldspar particles.

Laser vaporization of cirrus-like ice particles with secondary ice multiplication.

We investigate the interaction of ultrashort laser filaments with individual 90-µm ice particles, representative of cirrus particles. The ice particles fragment under laser illumination. By monitoring the evolution of the corresponding ice/vapor system at up to 140,000 frames per second over 30 ms, we conclude that a shockwave vaporization supersaturates the neighboring region relative to ice, allowing the nucleation and growth of new ice particles, supported by laser-induced plasma photochemistry. This process constitutes the first direct observation of filament-induced secondary ice multiplication, a process that strongly modifies the particle size distribution and, thus, the albedo of typical cirrus clouds.

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles.

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO4). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Light modulation in planar aligned short-pitch deformed-helix ferroelectric liquid crystals.

We study both experimentally and theoretically modulation of light in a planar aligned deformed-helix ferroelectric liquid crystal (DHFLC) cell with subwavelength helix pitch, which is also known as a short-pitch DHFLC. In our experiments, the azimuthal angle of the in-plane optical axis and electrically controlled parts of the principal in-plane refractive indices are measured as a function of voltage applied across the cell. Theoretical results giving the effective optical tensor of a short-pitch DHFLC expressed in terms of the smectic tilt angle and the refractive indices of the ferroelectric liquid crystal (FLC) are used to fit the experimental data. The optical anisotropy of the FLC material is found to be weakly biaxial. For both the transmissive and reflective modes, the results of fitting are applied to model the phase and amplitude modulation of light in the DHFLC cell. We demonstrate that if the thickness of the DHFLC layer is about 50µm, the detrimental effect of field-induced rotation of the in-plane optical axes on the characteristics of an axicon designed using the DHFLC spatial light modulator in the reflective mode is negligible.

Optics of short-pitch deformed-helix ferroelectric liquid crystals: symmetries, exceptional points, and polarization-resolved angular patterns.

In order to explore electric-field-induced transformations of polarization singularities in the polarization-resolved angular (conoscopic) patterns emerging after deformed-helix ferroelectric liquid crystal (DHFLC) cells with subwavelength helix pitch, we combine the transfer matrix formalism with the results for the effective dielectric tensor of biaxial FLCs evaluated using an improved technique of averaging over distorted helical structures. Within the framework of the transfer matrix method, we deduce a number of symmetry relations and show that the symmetry axis of L lines (curves of linear polarization) is directed along the major in-plane optical axis which rotates under the action of the electric field. When the angle between this axis and the polarization plane of incident linearly polarized light is above its critical value, the C points (points of circular polarization) appear in the form of symmetrically arranged chains of densely packed star-monstar pairs. We also emphasize the role of phase singularities of a different kind and discuss the enhanced electro-optic response of DHFLCs near the exceptional point where the condition of zero-field isotropy is fulfilled.

Enhanced orientational Kerr effect in vertically aligned deformed helix ferroelectric liquid crystals.

We disclose the vertically aligned deformed helix ferroelectric liquid crystal whose Kerr constant (Kkerr≈130 nm/V2 at λ=543 nm) is around one order of magnitude higher than any other value previously reported for liquid crystalline structures. Under certain conditions, the phase modulation with ellipticity less than 0.05 over the range of continuous and hysteresis-free electric adjustment of the phase shift from zero to 2π has been obtained at subkilohertz frequency.

Light-induced pitch transitions in photosensitive cholesteric liquid crystals: effects of anchoring energy.

We experimentally study how the cholesteric pitch P depends on the equilibrium pitch P0 in planar liquid crystal (LC) cells with both strong and semistrong anchoring conditions. The cholesteric phase was induced by dissolution in the nematic LC of the right-handed chiral dopant 7-dehydrocholesterol (7-DHC, provitamin D3) which transforms to left-handed tachysterol under the action of uv irradiation at the wavelength of 254 nm. By using the model of photoreaction kinetics we obtain the dependencies of isomer concentrations and, therefore, of the equilibrium pitch on the uv irradiation dose. The cholesteric pitch was measured as a function of irradiation time using the polarimetry method. In this method, the pitch is estimated from the experimental data on the irradiation time dependence of the ellipticity of light transmitted through the LC cells. It is found that the resulting dependence of the twist parameter 2D/P (D is the cell thickness) on the free twisting number parameter 2D/P0 shows jumplike behavior and agrees well with the known theoretical results for the anchoring potential of Rapini-Papoular form.