Charge Regulation Research Articles

Nanoscale topotactic phase transformation modulated by triboelectrification for high memory storage

The applications of triboelectrification have attracted much attention due to the direct regulation of charges with external mechanical stimuli. Atomic force microscopy (AFM) is an effective method to achieve controllable nanoscale friction. Herein, we demonstrated a phase transformation from the brownmillerite SrCoO2.5 (BM-SCO) to perovskite SrCoO3-δ (PV-SCO) as modulated by nanoscale friction with the contact mode AFM. Besides, such phase transformation can be reversible by applying a negative voltage. More importantly, when defining the surface potential of different phases as binary bits of “1” and “0”, we could reach high-density data storage as the surface charge is constantly written and erased in nanoscale regions. This work opens a new way for the regulation of phase transformation by triboelectrification, and realizes the surface charge patterning based on different phases at the nanoscale by AFM tip friction, which is of great significance for the application of nano devices in high-density data storage.

Uncovering the Contributions of Charge Regulation to the Stability of Single Alpha Helices.

The single alpha helix (SAH) is a recurring motif in biology. The consensus sequence has a di-block architecture that includes repeats of four consecutive glutamate residues followed by four consecutive lysine residues. Measurements show that the overall helicity of sequences with consensus E4 K4 repeats is insensitive to a wide range of pH values. Here, we use the recently introduced q-canonical ensemble, which allows us to decouple measurements of charge state and conformation, to explain the observed insensitivity of SAH helicity to pH. We couple the outputs from separate measurements of charge and conformation with atomistic simulations to derive residue-specific quantifications of preferences for being in an alpha helix and for the ionizable residues to be charged vs. uncharged. We find a clear preference for accommodating uncharged Glu residues within internal positions of SAH-forming sequences. The stabilities of alpha helical conformations increase with the number of E4 K4 repeats and so do the numbers of accessible charge states that are compatible with forming conformations of high helical content. There is conformational buffering whereby charge state heterogeneity buffers against large-scale conformational changes thus making the overall helicity insensitive to large changes in pH. Further, the results clearly argue against a single, rod-like alpha helical conformation being the only or even dominant conformation in the ensembles of so-called SAH sequences.

Surface charge regulation using classical density functional theory: the effect of divalent potential determining ions.

The charge regulation approach has been used to describe the charge of surfaces susceptible to the presence of protons and other ions. Conventionally, this model is used with the Poisson-Boltzmann equation, which generally neglects the finite size of the ions and the electrostatic correlations. Recently, progress has been made by coupling charge regulation with classical density functional theory (DFT), which explicitly includes these correlations. However, little is known about charge regulation at surfaces with both acid-base equilibria and complexation with multivalent ions. The main purpose of this work is to investigate the role divalent ions play in charge regulation. Using DFT, we show that the size of the divalent ion has significant consequences on the surface charge density and it should not be neglected. For the surface reactions investigated, the larger the size of the divalent cation, the greater the charge on the surface due to higher divalent concentration there. At low divalent concentration, the ion correlations play a second-order but non-negligible role; using Poisson-Boltzmann theory with point ions cannot recover the DFT surface charge. At high concentrations, ion correlations play a dominant role by creating charge inversion.

Control and regulation of skyrmionic topological charge in a novel synthetic antiferromagnetic nanostructure.

Skyrmionium is a combination of a skyrmion with a topological charge (Q is +1 or -1), resulting in a magnetic configuration with a total topological charge of Q = 0. Skyrmionium has distinctive characteristics, including a slightly higher velocity, motion restricted to the middle of the track without the skyrmion Hall effect (SkHE), and absence of an acceleration phase. However, there is little stray field due to the zero net magnetization, the topological charge Q is zero due to the magnetic configuration, and detecting skyrmionium is still challenging. In the present work, we propose a novel nanostructure composed of triple nanowires with a narrow channel. It was found that the skyrmionium is converted into a DW pair or skyrmion by the concave channel. It was also found that the topological charge Q can be regulated by Ruderman-Kittel-Kasuya-Yosida (RKKY) antiferromagnetic (AFM) exchange coupling. Moreover, we analyzed the mechanism of the function based on the Landau-Lifshitz-Gilbert (LLG) equation and energy variation and constructed a deep spiking neural network (DSNN) with a recognition accuracy of 98.6% with supervised learning via the spike timing dependent plasticity rule (STDP) by considering the nanostructure as an artificial synapse device corresponding to the electrical properties of the nanostructure. These results provide the means for skyrmion-skyrmionium hybrid application and neuromorphic computing applications.

Porous amorphous metal-organic frameworks based on heterotopic triangular ligands for iodine and high-capacity dye adsorption.

The research on amorphous metal-organic frameworks (aMOFs) is still in its infancy, and designing and constructing aMOFs with functional pores remains a challenge. Two aMOFs based on Co(II) and heterotopic triangular ligands with large conjugated aromatic planes, namely aMOF-1 and aMOF-2, were constructed and characterized by IR, XPS, EA, ICP, XANS and so on. aMOF-1 possesses mesopores, whereas aMOF-2 possesses micropores. The porosity, conjugated aromatic plane and uncoordinated N atoms in the framework allow these aMOFs to adsorb iodine and dyes. The iodine adsorption capacity of aMOF-1 is 3.3 g per g, which is higher than that of aMOF-2 (0.56 g per g), mainly due to the expansion or swelling of aMOF-1 after iodine adsorption. The uptake of cationic dyes by aMOF-2 showed more rapid kinetics and a higher removal rate than that by aMOF-1, mainly due to the difference in the porosity and surface charge. Although the surface charges of aMOF-1 and aMOF-2 are negative, both of them showed significantly faster adsorption kinetics toward anionic dyes, among which methyl orange (MO) and Congo red (CR) can be removed in 5 min. This occurs possibly because the quick adsorption of Na+ ions alters the surface charge of the framework and promotes dye uptake. The adsorption capacities of aMOF-1 for MO and CR reached 921 and 2417 mg g-1, respectively. The correlation data for aMOF-2 are 1042 and 1625 mg g-1, respectively. All adsorption capacities are among the highest compared to many cMOFs. Adsorption in mixed dye solution is found to be charge-dependent, kinetic-dependent, and synergetic in these systems. The porosity, surface charge regulation during adsorption, weak interactions and multiple adsorption processes contribute to the dye adsorption performance.

Charging station control strategy considering dynamic behaviour of electric vehicles with variable state of charge regulation for energy management of autonomous micro-grid

The electric vehicles (EVs) connected to the charging stations (CSs), as a part of autonomous micro-grid (MG), introduce additional fluctuations due to their dynamic behaviour owing to variable state of charge (SOC) and the type of EV. This paper puts forth the charging station control strategy (CSCS) for proper energy management (EM) and voltage regulation (VR) in an autonomous MG subjected to dynamic behaviour of EVs, fluctuations of solar irradiance, wind speed, and load. The EVs parked in the CSs either charge or discharge through two-way power exchange between the autonomous MG system and the CSs, depending on the generation and load demand distinctions. As a result, EVs that enter and depart the CSs may have varying battery voltage ratings and upper SOC limits that differ. The simulations are executed using the MATLAB® software, and the efficiency of the proposed CSCS is assessed in two different modes: excess power mode (EPM) and deficient power mode (DPM). For a realistic proposal analysis, the results are also checked using a hardware-in the-loop (HIL) real-time OPAL-RT simulator (OP5700). By comparing and contrasting the results obtained with MATLAB® and the OPAL-RT simulator, the proposed control strategy is validated.

Working Fluid Distribution and Charge Regulation Control in Organic Rankine Cycle

Working Fluid Distribution and Charge Regulation Control in Organic Rankine Cycle

Spatial correlated vortex arrays.

Spatial correlated vortex arrays may form in the same beam when a random source contains multiple helical phase structures. We introduced two types of partially coherent sources with Cartesian and polar symmetric helical phase structure and reveal the characteristics of their radiated fields, respectively. It is demonstrated that far fields generated by these families of sources carry interesting features through the joint regulation of coherence and topological charge, being lattice-like vortex patterns with adjustable dimension and shape.

Modeling Analysis of Superbuck Converter in Dual-Loop Competition Control

A Battery Charge Regulator system based on the Superbuck converter is presented, the working principle of the Superbuck converter is analyzed and the small signal model is established. In order to meet the requirements of wide input range and high dynamic response of the Superbuck converter, a double closed-loop control system is designed with output voltage and output current dual loop control as outer loop and input current control as inner loop. The stability of the control loop is verified by the Bode plot, and the simulation result of the system in two working conditions are given to support the theoretical analysis.

Charging of Dielectric Surfaces in Contact with Aqueous Electrolytes─the Influence of CO2.

The charge state of dielectric surfaces in aqueous environments is of fundamental and technological importance. Here, we study the influence of dissolved molecular CO2 on the charging of three chemically different surfaces (SiO2, Polystyrene, Perfluorooctadecyltrichlorosilane). We determine their charge state from electrokinetic experiments. We compare an ideal, CO2-free reference system to a system equilibrated against ambient CO2 conditions. In the reference system, the salt-dependent decrease of the magnitudes of ζ-potentials follows the expectations for a constant charge scenario. In the presence of CO2, the starting potential is lower by some 50%. The following salt-dependent decrease is weakened for SiO2 and inverted for the organic surfaces. We show that screening and pH-driven charge regulation alone cannot explain the observed effects. As an additional cause, we tentatively suggest dielectric regulation of surface charges due to a diffusively adsorbed thin layer of molecular CO2. The formation of such a dynamic layer, even at the hydrophilic and partially ionized silica surfaces, is supported by a minimal theoretical model and results from molecular simulations.

Theory of Charge Regulation of Colloidal Particles in Electrolyte Solutions

We present a theory that enables us to (i) calculate the effective surface charge of colloidal particles and (ii) efficiently obtain titration curves for different salt concentrations. The theory accounts for the shift of pH of solution due to the presence of 1:1 electrolyte. It also accounts self-consistently for the electrostatic potential produced by the deprotonated surface groups. To examine the accuracy of the theory, we have performed extensive reactive Monte Carlo simulations, which show excellent agreement between theory and simulations without any adjustable parameters.

Power system stability improvement considering drive train oscillations of virtual synchronous generator‐regulated type‐4 wind turbines

The type-4 wind turbine generators (WTGs) can provide inertial frequency response by implementing the virtual synchronous generator (VSG) concept. However, unstable torsional oscillations (TOs) would be induced in the multi-mass-spring drive-train which can destabilize the entire power system. In this study, participation factor analyses are performed for a power system inclusive of a thermal unit and aggregated WTG system. The system's eigenvalues are characterized and the possible detrimental impacts of TOs on the inertia provision process and overall power system stability are demonstrated and the related stability limits are identified. A comprehensive active torsional oscillations damper (CA-TOD) and a supercapacitor-based energy storage system (ESS) are presented and discussed to implement the CA-TOD. A state of charge (SoC) regulator is also employed to set the reference speed difference for the turbine-generator. Small-signal studies and electro-magnetic transient (EMT) simulations are performed to evaluate the functionality of the CA-TOD and SoC controller and estimate their impacts on the system's dynamics. The robust performance of the CA-TOD is compared to the band-pass filter-based TOD by sweeping key control parameters of the VSG and emulating drive-train parameter uncertainty. Key results are cross-verified by EMT simulations of a multimachine power system.

Predictive Diagnosis Based on Predictor Symptoms for Isolated Photovoltaic Systems Using MPPT Charge Regulators.

In this work, new results are presented on the implementation of predictive diagnosis techniques on isolated photovoltaic (PV) systems and installations. The novelties introduced in this research focus on the additional advantages obtained from the point of view of predictive diagnosis of faults caused by partial shading in isolated PV installations using maximum power point tracking (MPPT) regulators. MPPT regulators are comparatively more appropriate than pulse width modulation (PWM) solar regulators in order to implement fault diagnosis systems. MPPT regulators have a physical separation between the electrical parameters belonging to the part of the solar panel with respect to the batteries part. Therefore, these electrical parameters can be used to obtain early predictive symptoms of the effects of partial shading with a greater level of observation and sensitivity. Additionally, modifications are proposed in the PV system assembly to obtain greater homogeneity of all the panels regarding the solar irradiance reception angle.

Electrical Conductance of Charged Nanopores.

A nanopore’s response to an electrical potential drop is characterized by its electrical conductance, . For the last two decades, it has been thought that at low electrolyte concentrations, , the conductance is concentration-independent such that . It has been recently demonstrated that surface charge regulation changes the dependency to , whereby the slope typically takes the values α = 1/3 or 1/2. However, experiments have observed slopes of 2/3 and 1 suggesting that additional mechanisms, such as convection and slip-lengths, appear. Here, we elucidate the interplay between three mechanisms: surface charge regulation, convection, and slip lengths. We show that the inclusion of convection does not change the slope, and when the effects of hydrodynamic slip are included, the slope is doubled. We show that when all effects are accounted for, α can take any value between 0 and 1 where the exact value of the slope depends on the material properties. This result is of utmost importance in designing any electro-kinetically driven nanofluidic system characterized by its conductance.

Spatiotemporal dynamics of membrane surface charge regulates cell polarity and migration.

During cell migration and polarization, numerous signal transduction and cytoskeletal components self-organize to generate localized protrusions. Although biochemical and genetic analyses have delineated many specific interactions, how the activation and localization of so many different molecules are spatiotemporally orchestrated at the subcellular level has remained unclear. Here we show that the regulation of negative surface charge on the inner leaflet of the plasma membrane plays an integrative role in the molecular interactions. Surface charge, or zeta potential, is transiently lowered at new protrusions and within cortical waves of Ras/PI3K/TORC2/F-actin network activation. Rapid alterations of inner leaflet anionic phospholipids-such as PI(4,5)P2, PI(3,4)P2, phosphatidylserine and phosphatidic acid-collectively contribute to the surface charge changes. Abruptly reducing the surface charge by recruiting positively charged optogenetic actuators was sufficient to trigger the entire biochemical network, initiate de novo protrusions and abrogate pre-existing polarity. These effects were blocked by genetic or pharmacological inhibition of key signalling components such as AKT and PI3K/TORC2. Conversely, increasing the negative surface charge deactivated the network and locally suppressed chemoattractant-induced protrusions or subverted EGF-induced ERK activation. Computational simulations involving excitable biochemical networks demonstrated that slight changes in feedback loops, induced by recruitment of the charged actuators, could lead to outsized effects on system activation. We propose that key signalling network components act on, and are in turn acted upon, by surface charge, closing feedback loops, which bring about the global-scale molecular self-organization required for spontaneous protrusion formation, cell migration and polarity establishment.

Enabling stable 4.6 V LiCoO2 cathode through oxygen charge regulation strategy

LiCoO2 is the preferred cathode material for consumer electronic products due to its high volumetric energy density. However, the unfavorable phase transition and surface oxygen release limits the practical application of LiCoO2 at a high-voltage of 4.6 V to achieve a higher energy density demanded by the market. Herein, both bulk and surface structures of LiCoO2 are stabilized at 4.6 V through oxygen charge regulation by Gd-gradient doping. The enrichment of highly electropositive Gd on LiCoO2 surface will increase the effective charge on oxygen and improve the oxygen framework stability against oxygen loss. On the other hand, Gd ions occupy theCo-sites and suppress the unfavorable phase transition and micro-crack. The modified LiCoO2 exhibits superior cycling stability with capacity retention of 90.1% over 200 cycles at 4.6 V, and also obtains a high capacity of 145.7 mAh/g at 5 C. This work shows great promise for developing high-voltage LiCoO2 at 4.6 V and the strategy could also contribute to optimizing other cathode materials with high voltage and large capacity, such as cobalt-free high-nickel and lithium-rich manganese-based cathode materials.

Interfacial charge regulation of β-In2S3 photoanode via Tm3+ doping toward enhanced photoelectrochemical performance

The photoelectrochemical properties of the β-In2S3 are seriously restricted by the severe electron-hole pairs recombination. Introducing foreign ions is a powerful means to regulate the properties of β-In2S3, because of its special defect spinel structure. There are few reports that rare earth ion doped β-In2S3 nanosheets improve their photoelectrochemical properties. Herein, a novel nanostructure photoanode was fabricated using Tm3+ doped β-In2S3 by one-pot in situ hydrothermal method. The photoelectrochemical performance has the highest enhancement when the mole ratio of Tm3+ is 1%. The experimental results indicate that the carrier separation and injection efficiency of β-In2S3 after Tm3+ doping are increased to 8.34% and 76.11%, respectively. The introduction of Tm3+ in the β-In2S3 may yield plenty of shallow electron capture levels below conduction band minimum, which can capture photogenerated electrons to promote the separation of electron-hole pair and improve the photoelectrochemical properties of In2S3. This work sheds light on the rare earth ions doped semiconductor photoanode for photoelectrochemical application.

Influence of Membrane Permittivity on Charge Regulation of Weak Polyelectrolytes End-Tethered in Nanopores

Influence of Membrane Permittivity on Charge Regulation of Weak Polyelectrolytes End-Tethered in Nanopores

Thermodynamics of Charge Regulation during Ion Transport through Silica Nanochannels.

Ion-surface interactions can alter the properties of nanopores and dictate nanofluidic transport in engineered and biological systems central to the water-energy nexus. The ion adsorption process, known as "charge regulation", is ion-specific and is dependent on the extent of confinement when the electric double layers (EDLs) between two charged surfaces overlap. A fundamental understanding of the mechanisms behind charge regulation remains lacking. Herein, we study the thermodynamics of charge regulation reactions in 20 nm SiO2 channels via conductance measurements at various concentrations and temperatures. The effective activation energies (Ea) for ion conductance at low concentrations (strong EDL overlap) are ∼2-fold higher than at high concentrations (no EDL overlap) for the electrolytes studied here: LiCl, NaCl, KCl, and CsCl. We find that Ea values measured at high concentrations result from the temperature dependence of viscosity and its influence on ion mobility, whereas Ea values measured at low concentrations result from the combined effects of ion mobility and the enthalpy of cation adsorption to the charged surface. Notably, the Ea for surface reactions increases from 7.03 kJ mol-1 for NaCl to 16.72 ± 0.48 kJ mol-1 for KCl, corresponding to a difference in surface charge of -8.2 to -0.8 mC m-2, respectively. We construct a charge regulation model to rationalize the cation-specific charge regulation behavior based on an adsorption equilibrium. Our findings show that temperature- and concentration-dependent conductance measurements can help indirectly probe the ion-surface interactions that govern transport and colloidal interactions at the nanoscale─representing a critical step forward in our understanding of charge regulation and adsorption phenomena under nanoconfinement.

Electrostatic Features for the Receptor Binding Domain of SARS-COV-2 Wildtype and Its Variants. Compass to the Severity of the Future Variants with the Charge-Rule.

Electrostatic intermolecular interactions are important in many aspects of biology. We have studied the main electrostatic features involved in the interaction of the receptor-binding domain (RBD) of the SARS-CoV-2 spike protein with the human receptor Angiotensin-converting enzyme 2 (ACE2). As the principal computational tool, we have used the FORTE approach, capable to model proton fluctuations and computing free energies for a very large number of protein-protein systems under different physical-chemical conditions, here focusing on the RBD-ACE2 interactions. Both the wild-type and all critical variants are included in this study. From our large ensemble of extensive simulations, we obtain, as a function of pH, the binding affinities, charges of the proteins, their charge regulation capacities, and their dipole moments. In addition, we have calculated the pKas for all ionizable residues and mapped the electrostatic coupling between them. We are able to present a simple predictor for the RBD-ACE2 binding based on the data obtained for Alpha, Beta, Gamma, Delta, and Omicron variants, as a linear correlation between the total charge of the RBD and the corresponding binding affinity. This "RBD charge rule" should work as a quick test of the degree of severity of the coming SARS-CoV-2 variants in the future.