Linear and Nonlinear Dielectric Response of Intrinsically Disordered Proteins.

Linear and nonlinear dielectric responses of solutions of intrinsically disordered proteins (IDPs) were analyzed by combining molecular dynamics simulations with formal theories. A large increment of the linear dielectric function over that of the solvent is found and related to large dipole moments of IDPs. The nonlinear dielectric effect (NDE) of the IDP far exceeds that of the bulk electrolyte, offering a route to interrogate protein conformational and rotational statistics and dynamics. Conformational flexibility of the IDP makes the dipole moment statistics consistent with the gamma/log-normal distributions and contributes to the NDE through the dipole moment's non-Gaussian parameter. The intrinsic non-Gaussian parameter of the dipole moment combines with the protein osmotic compressibility in the nonlinear dielectric susceptibility when dipolar correlations are screened by the electrolyte. The NDE is dominated by dipolar correlations when electrolyte screening is reduced.

Colorimetric detection of electrolyte ions in blood based on biphasic microdroplet extraction.

BACKGROUND: Timely diagnosis and prevention of diseases require rapid and sensitive detection of biomarkers from blood samples without external interference. Abnormal electrolyte ion levels in the blood are closely linked to various physiological disorders, including hypertension. Therefore, accurate, interference-free, and precise measurement of electrolyte ion concentrations in the blood is particularly important. RESULTS: In this work, a colorimetric sensor based on a biphasic microdroplet extraction is proposed for the detection of electrolyte ions in the blood. This sensor employs mini-pillar arrays to facilitate contact between adjacent blood microdroplets and organic microdroplets serving as sensing phases, with any color changes being monitored through a smartphone's colorimetric software. The sensor is highly resistant to interference and does not require pre-treatment of the blood samples. Remarkably, the sensor exhibits exceptional reliability and stability, allowing for rapid enrichment and detection of K+, Na+, and Cl- in the blood within 10 s (Cl-), 15 s (K+) and 40 s (Na+) respectively. SIGNIFICANCE: The colorimetric sensor based on biphasic microdroplet extraction offers portability due to its compact size and ease of operation without the need for large instruments. Additionally, it is location-independent, making it a promising tool for real-time biomarker detection in body fluids such as blood.

Fully Integrated Multiplexed Wristwatch for Real-Time Monitoring of Electrolyte Ions in Sweat.

Considerable progress has already been made in sweat sensors based on electrochemical methods to realize real-time monitoring of biomarkers. However, realizing long-term monitoring of multiple targets at the atomic level remains extremely challenging, in terms of designing stable solid contact (SC) interfaces and fully integrating multiple modules for large-scale applications of sweat sensors. Herein, a fully integrated wristwatch was designed using mass-manufactured sensor arrays based on hierarchical multilayer-pore cross-linked N-doped porous carbon coated by reduced graphene oxide (NPCs@rGO-950) microspheres with high hydrophobicity as core SC, and highly selective monitoring simultaneously for K+, Na+, and Ca2+ ions in human sweat was achieved, exhibiting near-Nernst responses almost without forming an interfacial water layer. Combined with computed tomography, solid-solid interface potential diffusion simulation results reveal extremely low interface diffusion potential and high interface capacitance (598 µF), ensuring the excellent potential stability, reversibility, repeatability, and selectivity of sensor arrays. The developed highly integrated-multiplexed wristwatch with multiple modules, including SC, sensor array, microfluidic chip, signal transduction, signal processing, and data visualization, achieved reliable real-time monitoring for K+, Na+, and Ca2+ ion concentrations in sweat. Ingenious material design, scalable sensor fabrication, and electrical integration of multimodule wearables lay the foundation for developing reliable sweat-sensing systems for health monitoring.

Molecular dynamics simulation study of sodium ion structure & dynamics in water in ionic liquids electrolytes using 1-butyl-3-methyl imidazolium tetrafluoroborate and 1-butyl-3-methyl imidazolium hexafluorophosphate.

In this paper, we have performed an all-atom molecular dynamics simulation to understand the structure and dynamics of Na+ ions in water mixed Ionic liquids (Water in Ionic liquid). Two ionic liquid (IL) systems consist of (1) 1-butyl-3-methylimidazolium [BMIM] tetrafluoroborate [BF4] and (2) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF6] were considered in this work. We understand various inter-molecular structures and dynamic and thermodynamic behaviours of Na+ ions in the water-mixed IL systems. The water (H2O) mole fractions (x) varied from 0.33 to 0.71. The neat ILs [BMIM][BF4] and [BMIM][PF6] pairwise radial distribution functions show a decrease with an increase in x. The [BMIM][PF6] exhibits a strong coordination structure with Na+ ions across the entire range of x values. The rdf between the pairs of Na+-[PF6] presents a significant interaction compared to Na+ and [BF4]. The Na + ions manifested greater coordination with H2O In H2O-[BMIM][PF6] compared to H2O-[BMIM][BF4]. The self-diffusion coefficient (D) values of Na + ions increase with the rise in x in both ILs. The D values of Na + ions are 10-fold higher in [BMIM][BF4] than [BMIM][PF6]. The ionic conductivity values are higher for [BMIM][BF4]. Overall, this paper unveils molecular-level insights for understanding the behavior of Na+ ions in the water in ionic liquid systems.

Electrochemical Characterization of Diffusion in Polymeric vs. Monomeric Solvents.

Polymer electrolyte was used as a medium for testing the performance of microband electrodes under conditions of linear diffusion. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments were performed in a highly viscous medium, where diffusion rates are much slower than in fluid solutions. The log i vs. log v (CV) or log i vs. log t (CA) relationships with the current equation confirmed the existence of such conditions, yielding slope values that were lower than the expected 0.5. This could indicate an impure linear diffusion profile, i.e., some contribution from radial diffusion (edge effects). However, the desired value of 0.5 was obtained when performing these tests in monomeric solvents of similar viscosities, such as glycerol or propylene glycol. These results led to the conclusion that the current equations, which are based on Fick's laws, may not be applicable for polymer electrolytes, where various obstructions to free diffusion result in a more complicated process than for monomeric solvents.

Adaptively resettable microfluidic patch for sweat rate and electrolytes detection.

Skin-interfaced microfluidic patch has become a reliable device for sweat collection and analysis. However, the intractable problems of emptying the microchannel for reuse, and the channel's volumetric capacity limited by the size of the patch, directly hinder the practical application of sweat sensors. Herein, we report an adaptively resettable microfluidic sweat patch (Art-Sweat patch) capable of continuously monitoring both sweat rate (0.2-4.0 µL min-1) and total ionic charge concentration (10-200 mmol L-1). We develop a platform with a vertical and horizontal microchannel combined strategy, enabling repeatedly filling sweat and emptying the microchannel for autonomously resetting and detecting. The variation in the emptied volume is designed to be adaptively identified by the sensor, resulting in enhanced stability and an enlarged volumetric capacity of over 300 µL. By integrating with self-designed wireless transmission modules, the proposed Art-Sweat patch shows product-level wearability and high performance in monitoring variations in regional sweat rate and concentration for hydration status assessment.

Artificial Funnel Nanochannel Device Emulates Synaptic Behavior.

Creating artificial synapses that can interact with biological neural systems is critical for developing advanced intelligent systems. However, there are still many difficulties, including device morphology and fluid selection. Based on Micro-Electro-Mechanical System technologies, we utilized two immiscible electrolytes to form a liquid/liquid interface at the tip of a funnel nanochannel, effectively enabling a wafer-level fabrication, interactions between multiple information carriers, and electron-to-chemical signal transitions. The distinctive ionic transport properties successfully achieved a hysteresis in ionic transport, resulting in adjustable multistage conductance gradient and synaptic functions. Notably, the device is similar to biological systems in terms of structure and signal carriers, especially for the low operating voltage (200 mV), which matches the biological neural potential (∼110 mV). This work lays the foundation for realizing the function of iontronics neuromorphic computing at ultralow operating voltages and in-memory computing, which can break the limits of information barriers for brain-machine interfaces.

Mimicking Bidirectional Inhibitory Synapse Using a Porous-Confined Ionic Memristor with Electrolyte/Tris(4-aminophenyl)amine Neurotransmitter.

Ionic memristors can emulate brain-like functions of biological synapses for neuromorphic technologies. Apart from the widely studied excitatory-excitatory and excitatory-inhibitory synapses, reports on memristors with the inhibitory-inhibitory synaptic behaviors remain a challenge. Here, the first biaxially inhibited artificial synapse is demonstrated, consisting of a solid electrolyte and conjugated microporous polymers bilayer as neurotransmitter, with the former serving as an ion reservoir and the latter acting as a confined transport. Due to the migration, trapping, and de-trapping of ions within the nanoslits, the device poses inhibitory synaptic plasticity under both positive and negative stimuli. Remarkably, the artificial synapse is able to maintain a low level of stable nonvolatile memory over a long period of time (≈60 min) after multiple stimuli, with feature-inferencing/-training capabilities of neural node in neuromorphic computing. This work paves a reliable strategy for constructing nanochannel ionic memristive materials toward fully inhibitory synaptic devices.

Ionic Distribution of an Unequal Electrolyte Near an Air/Water Surface.

The distribution of electrolytes near the air/water surface plays an essential role in many processes. While the general distribution is governed by classic Poisson-Boltzmann statistics, the analytical solution is only available for symmetric electrolytes. From the recent studies in the literature, it is evident that surface adsorption is dependent on specific ions as well as the H-bond structure at the surface. Experimental data can capture the macro properties of the surface, such as surface tension and surface potential. Yet, the underpinning mechanisms behind this experimental macro-observation remain unclear. To address the challenge, we developed a framework combining experimental studies and numerical calculations. The model was developed for electrolytes with unequal cationic and anionic charges. The asymmetric model was successfully applied to describe the surface charge of MgCl 2 aqueous solution. The results can be explained by the role of cationic size and charge on the surface layer.

Chitosan as a suitable host for sustainable plasticized nanocomposite sodium ion conducting polymer electrolyte in EDLC applications: Structural, ion transport and electrochemical studies.

The challenge in front of EDLC device is their low energy density compared to their battery counter parts. In the current study, a green plasticized nanocomposite sodium ion conducting polymer blend electrolytes (PNSPBE) was developed by incorporating plasticized Chitosan (CS) blended with polyvinyl alcohol (PVA), doped with NaBr salt with various concentration of CaTiO3 nanoparticles. The most optimized PNSPBE film was subsequently utilized in an EDLC device to evaluate its effectiveness both as an electrolyte and a separator. Structural and morphological changes were assessed using XRD and SEM techniques. The PNSPBE film demonstrated a peak ionic conductivity of 9.76×10-5 S/cm, as determined through EIS analysis. The dielectric and AC studies provided further confirmation of structural modifications within the sample. Both TNM and LSV analyses affirmed the suitability of the prepared electrolyte for energy device applications, evidenced by its adequate ion transference number and an electrochemical potential window of 2.86 V. Electrochemical properties were assessed via CV and GCD techniques, confirming non-Faradaic ion storage, indicated by the rectangular CV pattern at low scan rates. The parameters associated with the designed EDLC device including specific capacitance, ESR, power density (1950 W/kg) and energy density (12.3 Wh/kg) were determined over 1000 cycles.

Nonlinear Impact of Electrolyte Solutions on Protein Dynamics.

Halophilic organisms have adapted to multi-molar salt concentrations, their cytoplasmic proteins functioning despite stronger attraction between hydrophobic groups. These proteins, of interest in biotechnology because of decreasing fresh-water resources, have excess acidic amino acids. It has been suggested that conformational fluctuations - critical for protein function - decrease in the presence of a stronger hydrophobic effect, and that an acidic proteome would counteract this decrease. However, our understanding of the salt- and acidic amino acid dependency of enzymatic activity is limited. Here, using solution NMR relaxation and molecular dynamics simulations for in total 14 proteins, we show that salt concentration has a limited and moreover non-monotonic impact on protein dynamics. The results speak against the conformational-fluctuations model, instead indicating that maintaining protein dynamics to ensure protein function is not an evolutionary driving force behind the acidic proteome of halophilic proteins.

Conjugated Oligoelectrolyte with DNA Affinity for Enhanced Nuclear Imaging and Precise DNA Quantification.

Precise DNA quantification and nuclear imaging are pivotal for clinical testing, pathological diagnosis, and drug development. The detection and localization of mitochondrial DNA serve as crucial indicators of cellular health. We introduce a novel conjugated oligoelectrolyte (COE) molecule, COE-S3, featuring a planar backbone composed of three benzene rings and terminal side chains. This unique amphiphilic structure endows COE-S3 with exceptional water solubility, a high quantum yield of 0.79, and a significant fluorescence Stokes shift (λex = 366 nm, λem = 476 nm), alongside a specific fluorescence response to DNA. The fluorescence intensity correlates proportionally with DNA concentration. COE-S3 interacts with double-stranded DNA (dsDNA) through an intercalation binding mode, exhibiting a binding constant (K) of 1.32 × 106 M-1. Its amphiphilic nature and strong DNA affinity facilitate its localization within mitochondria in living cells and nuclei in apoptotic cells. Remarkably, within 30 min of COE-S3 staining, cell vitality can be discerned through real-time nuclear fluorescence imaging of apoptotic cells. COE-S3's high DNA selectivity enables quantitative intracellular DNA analysis, providing insights into cell proliferation, differentiation, and growth. Our findings underscore COE-S3, with its strategically designed, shortened planar backbone, as a promising intercalative probe for DNA quantification and nuclear imaging.

Synthesis and evaluation of cellulose/polypyrrole composites as polymer electrolytes for lithium-ion battery application.

Natural polymers as battery components have a number of advantages, including availability, biodegradability, unleakage, stable form, superior process, electrochemical stability, and low cost. In other sides, conductive polymers can improve the electrochemical properties of the battery, such as charge/discharge rates, cycling stability, and overall energy storage capacity. Therefore, the combination of these two materials can provide acceptable features. In this study, polymer electrolytes based on cellulose have been synthesized by solution casting method to prepare a thin polymer film. Then, polypyrrole (PPy) was blended with cellulose in different weight ratios. To prevent electrical conductivity of blends, PPy was used <10 wt%. The electrochemical properties of prepared electrolytes have been investigated by different methods. The results showed that ionic conductivity was increased by addition of PPy to cellulose due to the creation of pores and also due to the high dielectric constant of conductive polymers. All synthesized electrolytes had suitable ionic conductivity (in the range of 10-3 S cm-1), significant charge capacity, stable cyclic performance, excellent electrochemical stability (above 4.8 V), and high cation transfer number (between 0.38 and 0.66 for pure cellulose and the sample containing 10 wt% PPy).

Unveiling the effects of protein corona formation on the aggregation kinetics of gold nanoparticles in monovalent and divalent electrolytes.

Elucidation of the aggregation behaviors of gold nanoparticles (AuNPs) in water systems is crucial to understanding their environmental fate and transport as well as human health effects. We investigated the early-stage aggregation kinetics of AuNPs coated by human serum albumin (HSA) protein corona (PC) in NaCl and CaCl2 through time-resolved dynamic light scattering. We found that the aggregation of PC-AuNPs depended on the concerted effects of electrolyte concentration, valence, and HSA concentration. At low HSA concentration (≤0.005 g/L), the aggregation kinetics of PC-AuNPs was similar to that of bare AuNPs due to insignificant HSA adsorption. At intermediate HSA concentrations of 0.025-0.050 g/L, the aggregation of PC-AuNPs was retarded in both electrolytes due to steric repulsive forces imparted by the PCs. Additionally, HSA PCs had a weaker retardation effect on PC-AuNPs aggregation in divalent than in monovalent electrolytes. Quartz crystal microbalance measurements revealed that the presence of Ca2+ promoted additional HSA adsorption on PC-AuNPs likely via -COO-Ca2+ bond, and eventually enhanced the aggregation between PC-AuNPs. High-concentration HSA (>0.5 g/L) resulted in no PC-AuNPs aggregation regardless of electrolyte valence and concentrations. Finally, desorption of HSA barely occurred after adsorption on the gold surface, suggesting that the formation of PC-AuNPs is mostly irreversible.

Enhancing microbial CO2 electrocatalysis for multicarbon reduction in a wet amine-based catholyte.

Microbial CO2 electroreduction (mCO2ER) offers a promising approach for producing high-value multicarbon reductants from CO2 by combining CO2 fixing microorganisms with conducting materials (i. e., cathodes). However, the solubility and availability of CO2 in an aqueous electrolyte pose significant limitations in this system. This study demonstrates the efficient production of long-chain multicarbon reductants, specifically carotenoids (~C40), within a wet amine-based catholyte medium during mCO2ER. Optimizing the concentration of the biocompatible CO2 absorbent, monoethanolamine (MEA), led to enhanced CO2 fixation in the electroautotroph bacteria. Molecular biological analyses revealed that MEA in the catholyte medium redirected the carbon flux towards carotenoid biosynthesis during mCO2ER. The faradaic efficiency of mCO2ER with MEA for carotenoid production was 4.5-fold higher than that of the control condition. These results suggest the mass transport bottleneck in bioelectrochemical systems could be effectively addressed by MEA-assissted mCO2ER, enabling highly efficient production of valuable products from CO2.

Ammonia removal and simultaneous immobilization of manganese and magnesium from electrolytic manganese residue by a low-temperature CaO roasting process.

A large amount of open-dumped electrolytic manganese residue (EMR) has posed a severe threat to the ecosystem and public health due to the leaching of ammonia (NH4+) and manganese (Mn). In this study, CaO addition coupled with low-temperature roasting was applied for the treatment of EMR. The effects of roasting temperature, roasting time, CaO-EMR mass ratio and solid-liquid ratio were investigated. The most cost-effective and practically viable condition was explored through response surface methodology. At a CaO: EMR ratio of 1:16.7, after roasting at 187 °C for 60 min, the leaching concentrations of NH4+ and Mn dropped to 10.18 mg/L and 1.05 mg/L, respectively, below their discharge standards. In addition, the magnesium hazard (MH) of EMR, which was often neglected, was studied. After treatment, the MH of the EMR leachate was reduced from 60 to 37. Mechanism analysis reveals that roasting can promote NH4+ to escape as NH3 and convert dihydrate gypsum to hemihydrate gypsum. Mn2+ and Mg2+ were mainly solidified as MnO2 and Mg(OH)2, respectively. This study proposes an efficient and low-cost approach for the treatment of EMR and provides valuable information for its practical application.

Ionic liquids: environmentally sustainable materials for energy conversion and storage applications.

Ionic liquids (ILs), often known as green designer solvents, have demonstrated immense application potential in numerous scientific and technological domains. ILs possess high boiling point and low volatility that make them suitable environmentally benign candidates for many potential applications. The more important aspect associated with ILs is that their physicochemical properties can be effectively changed for desired applications just by tuning the structure of the cationic and/or anionic part of ILs. Furthermore, these eco-friendly designer materials can function as electrolytes or solvents depending on the application. Owing to the distinctive properties such as low volatility, high thermal and electrochemical stability, and better ionic conductivity, ILs are nowadays immensely used in a variety of energy applications, particularly in the development of green and sustainable energy storage and conversion devices. Suitable ILs are designed for specific purposes to be used as electrolytes and/or solvents for fuel cells, lithium-ion batteries, supercapacitors (SCs), and solar cells. Herein, we have highlighted the utilization of ILs as unique green designer materials in Li-batteries, fuel cells, SCs, and solar cells. This review will enlighten the promising prospects of these unique, environmentally sustainable materials for next-generation green energy conversion and storage devices. Ionic liquids have much to offer in the field of energy sciences regarding fixing some of the world's most serious issues. However, most of the discoveries discussed in this review article are still at the laboratory research scale for further development. This review article will inspire researchers and readers about how ILs can be effectively applied in energy sectors for various applications as mentioned above.

Measurement of Anions in Tear Fluid Using Ion Chromatography.

PURPOSE: Tear fluid (TF) contains a variety of electrolytes that exhibit a strong correlation with its osmotic pressure. These electrolytes are also related to the etiology of diseases on ocular surfaces such as dry eye syndromes and keratopathy. Although positive ions (cations) in TF have been investigated to understand their roles, negative ions (anions) have hardly been studied because applicable analytical methods are restricted to a few kinds. In this study, we established a method to analyze the anions involved in a sufficiently small amount of TF for in situ diagnosis of a single subject. METHODS: Twenty healthy volunteers (10 men and 10 women) were recruited. Anions in their TF were measured on a commercial ion chromatograph (IC-2010, Tosoh, Japan). Tear fluid (5 µL or more) was collected from each subject with a glass capillary, diluted with 300 µL of pure water, and conveyed to the chromatograph. We successfully monitored the concentrations of bromide, nitrate, phosphate, and sulfate anions (Br - , NO 3- , HPO 42- , and SO 42- , respectively) in TF. RESULTS: Br - and SO 42- were universally detected in all samples, whereas NO 3- was found in 35.0% and HPO 42- in 30.0% of them. The mean concentrations (mg/L) of each anion were Br - , 4.69 ± 0.96; NO 3- , 0.80 ± 0.68; HPO 42- , 17.48 ± 7.60; and SO 42- , 3.34 ± 2.54. As for SO 42- , no sex differences or diurnal variations were observed. CONCLUSIONS: We established an efficient protocol to quantitate various inorganic anions involved in a small amount of TF using a commercially available instrument. This is the first step to elucidate the role of anions in TF.

Transformations in crystals of DNA-functionalized nanoparticles by electrolytes.

Colloidal crystals have applications in water treatments, including water purification and desalination technologies. It is, therefore, important to understand the interactions between colloids as a function of electrolyte concentration. We study the assembly of DNA-grafted gold nanoparticles immersed in concentrated electrolyte solutions. Increasing the concentration of divalent Ca2+ ions leads to the condensation of nanoparticles into face-centered-cubic (FCC) crystals at low electrolyte concentrations. As the electrolyte concentration increases, the system undergoes a phase change to body-centered-cubic (BCC) crystals. This phase change occurs as the interparticle distance decreases. Molecular dynamics analysis suggests that the interparticle interactions change from strongly repulsive to short-range attractive as the divalent-electrolyte concentration increases. A thermodynamic analysis suggests that increasing the salt concentration leads to significant dehydration of the nanoparticle environment. We conjecture that the intercolloid attractive interactions and dehydrated states favour the BCC structure. Our results gain insight into salting out of colloids such as proteins as the concentration of salt increases in the solution.

Organic micropollutant removal and phosphate recovery by polyelectrolyte multilayer membranes: Impact of buildup interactions.

Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes.