Ionic Strength Conditions Research Articles

Unveiling protein-protein interaction potential through Monte Carlo simulation combined with small-angle X-ray scattering

Protein interactions are investigated under different conditions of lysozyme concentration, temperature and ionic strength by means of in-solution small angle X-Ray scattering (SAXS) experiments and Monte Carlo (MC) simulations. Initially, experimental data were analysed through a Hard-Sphere Double Yukawa (HSDY) model combined with Random Phase Approximation (RPA), a closure relationship commonly used in the literature for monodisperse systems. We realized by means of MC that the HSDY/RPA modelling fails to describe the protein-protein pair potential for moderated and dense systems at low ionic strength, mainly due to inherent distortions of the RPA approximation. Our SAXS/MC results thus show that lysozyme concentrations between 2 (diluted) and 20 mg/mL (not crowded) present similar protein-protein pair potential preserving the values of surface net charge around 7 e, protein diameter of 28 Å, decay range of attractive well potential of 3 Å and a depth of the well potential varying from 1 to 5 kBT depending on temperature and salt addition. Noteworthy, we here propose a novel method to analyse the SAXS data from interacting proteins through MC simulations, which overcomes the deficiencies presented by the use of a closure relationship. Furthermore, this new methodology of combining SAXS with MC simulations gives a step forward to investigate more complex systems as those composed of a mixture of proteins of distinct species presenting different molecular weights (and hence sizes) and surface net charges at low, moderate and very dense systems.

Divalent cation contributions to the co-transport and deposition of functionalized multi-walled carbon nanotubes in porous media in the presence of bentonite or goethite nanoparticles: Experiment and simulation

This work investigates the influence of cation type (Ca2+ as compared to K+) on the co-transport and deposition of functionalized multi-walled carbon nanotubes (MWCNTs) with negatively (bentonite nanoparticles, BNPs) or positively (goethite nanoparticles, GNPs) charged natural nanoparticles under the same ionic strength (IS = 1 mM) conditions. In packed column tests with quartz sand (QS), the co-transport of MWCNTs was slightly increased by BNPs and inhibited by GNPs in both CaCl2 and KCl solutions, whereas the co-transport of BNPs or GNPs was facilitated by MWCNTs in both solutions. However, the co-transport of MWCNTs in the presence of BNPs or GNPs exhibited a different dependency on the cation type in quartz crystal microbalance with dissipation (QCM-D) tests. No deposition of MWCNTs and BNPs was observed in QCM-D studies in the presence of KCl, while enhanced deposition of MWCNTs and GNPs occurred in this same solution. In contrast, the deposition of both MWCNTs and BNPs or MWCNTs and GNPs increased in QCM-D in the presence of CaCl2. In both column and QCM-D studies, Ca2+ exhibited a more significant impact on co-transport than K+, especially for MWCNTs with GNPs than BNPs. Results from molecular dynamic simulations, aggregation studies, and interaction energy calculations indicate that non-DLVO interactions (e.g., H-bonding and cation-π interaction) between two nanoparticles (MWCNTs with BNPs or GNPs) played a non-negligible role in interpreting the deposition and co-transport in the presence of the divalent cation Ca2+. Mathematical modeling of breakthrough curves and retention profiles and aggregation results suggest that both straining and competitive blocking were enhanced and played dominant roles in the co-transport of MWCNTs in the presence of BNPs or GNPs in QS, especially in the presence of Ca2+. This work sheds novel insights on the contribution of divalent cations to interactions between two colloids and their co-transport in porous media. This information is needed to assess the environmental fate and risks of engineered nanoparticles (ENPs) and natural nanoparticles in aquatic and soil environments with abundant divalent cations.

Evaluating the efficacy of endolysins and membrane permeabilizers against Vibrio parahaemolyticus in marine conditions

Endolysins have garnered significant attention as a potential alternative to antibiotics in aquaculture, mainly for combating Vibrio spp., Gram-negative pathogens responsible for infectious outbreaks. However, endolysin effectiveness against Gram-negative bacteria is limited due to the outer membrane's poor permeability. The combat against marine pathogens poses an additional challenge of finding endolysins that retain their activity in high ionic strength conditions. Thus, this study aimed to demonstrate that certain endolysins retain muralytic activity in seawater and also evaluated outer membrane permeabilizers as endolysin adjuvants. The effectiveness of KZ144 and LysPA26 endolysins, along with EDTA and oregano essential oil, was evaluated against Vibrio parahaemolyticus ATCC-17802 in natural seawater. Results revealed the muralytic activity of both endolysins in seawater. However, the endolysins appeared to counteract the permeabilizers' effect during the initial bactericidal assays. Further investigations revealed that the observed effect was not antagonistic. After the permeabilizer action, V. parahaemolyticus likely used endolysins as a growth substrate. Endolysins may not play an indifferent role if they fail to exert a bactericidal effect. Instead, they can serve as a substrate for fast-growing bacteria, such as V. parahaemolyticus, increasing bacterial density. It should be considered a potential drawback of endolysins' proteinaceous nature as bactericidal agents.

Fluorescence Imaging of Nanoparticle Uptake into Liquid-Liquid Phase-Separated Droplets.

Liquid-liquid phase separation (LLPS) in living cells has received considerable attention in the biomedical research field. This study is the first to report nanoparticle (NP) uptake into LLPS droplets. Fluorescent dye, Nile red loaded polystyrene NPs (NR-PSt NPs) uptake into model LLPS droplets consisting of adenosine triphosphate (ATP) and poly-L-lysine (PLL) was visualized using fluorescence imaging. Fluorescence imaging showed that the LLPS droplets had a quick NP uptake behavior. Furthermore, temperature changes (4-37 °C) significantly affected the NP uptake behavior of the LLPS droplets. Moreover, the NP-incorporated droplets displayed high stability under strong ionic strength conditions (1 M NaCl). ATP measurements displayed that ATP was released from the NP-incorporated droplets, indicating that the weakly negatively charged ATP molecules and strongly negatively charged NPs were exchanged, which resulted in the high stability of the LLPS droplets. These fundamental findings will contribute to the LLPS studies using various NPs.

High ionic strength dissociation assay reduces dimeric target interference in immunogenicity testing.

Aim: The presence of di-/multi-meric forms of soluble target in biological samples can interfere in anti-drug antibody (ADA) assays, leading to increased background values and potentially false positivity. The authors investigated the use of the high ionic strength dissociation assay (HISDA) to reduce target interference in two different ADA assays. Results: Interference caused by homodimeric FAP was successfully eliminated to enable cut point determination after applying HISDA. Biochemical experiments confirmed the dissociation of homodimeric FAPafter treatment with high ionic strength conditions. Conclusion: HISDA is a promising approach to simultaneously achieve high drug tolerance and reduced interference by noncovalently bound dimeric target molecules in ADA assays without extensive optimization, which is particularly advantageous in routine use.

Peculiarities of oligomerization of smooth muscle titin and skeletal myosin-binding protein C

Protein oligomers are important intermediates in the formation of amyloid fibrils. In amyloidoses, for instance, in Alzheimer's disease, oligomers are able to exert toxic effects on cells. This paper describes the distinctive features of oligomerization of multidomain muscle proteins such as smooth muscle titin and myosin-binding protein C (MyBP-C) of skeletal muscles, which consist of FnIII-like and IgC2-like domains and form amorphous amyloid aggregates in vitro. MyBP-C at low ionic strength (below physiological values) formed stable oligomers that did not participate in further aggregation. In high ionic strength conditions (µ ~ 0.6), smooth muscle titin formed oligomers, which were precursors of amyloid amorphous aggregates of this protein. The results obtained help expand existing knowledge about the process of protein aggregation.

Effect of reduced inherent organic matter on stability and transport behaviors of black soil colloids

Soil organic matter plays an important role in the stability, transport, and fate of soil colloids. At present, studies have mostly focused on the effects of adding exogenous organic matter on soil colloidal properties, while there is very limited research on the effect of reduced inherent soil organic matter on the environmental behavior of soil colloids. This study investigated the stability and transport behavior of black soil colloids (BSC) and black soil colloids with reduced inherent organic matter (BSC-ROM) under different ionic strength (5, 50 mM) and background solution pH (4.0, 7.0, and 9.0) conditions. Meanwhile, the release behavior of two soil colloids in the saturated sand column under transient ionic strength conditions was also studied. The results showed that both ionic strength reduction and pH increase increased the negative charges of BSC and BSC-ROM, and improved the electrostatic repulsion between soil colloids and grain surface, thereby promoting the stability and mobility of soil colloids. The decrease in inherent organic matter had little effect on the surface charge of soil colloids, suggesting that the electrostatic repulsion was not the main force affecting the stability and mobility of BSC and BSC-ROM, and reducing inherent organic matter might significantly reduce the stability and mobility of soil colloids by weakening the steric hindrance interaction. The decrease of transient ionic strength reduced the depth of the energy minimum and activated the soil colloids retained on the surface of the grain at three pH conditions. This study is helpful to predict the potential impact of soil organic matter degradation on the fate of BSC in natural environment system.

Fabrication and characterization of succinylated and glycosylated soy protein isolate and its self-assembled nanogel

In this study, we used succinic anhydride (SA) acylation and dextran (DX) glycosylation modified soybean isolate protein (SPI) to develop self-assembled SPI-SA-DX adduct-based nanogels. Degree of modification, SDS-PAGE, and FT-IR studies showed that the amino group of the SPI was replaced by hydrophilic dextran and succinic acid carboxyl groups. Dextran chain and anhydride group attachment to the soybean protein surface enhanced hydrophilicity and spatial site blocking. Modification-induced protein structure unfolding, free sulfhydryl groups to be converted to disulfide bonds, and reduced surface hydrophobicity (H0). H0 was lowest at 33,750 ± 1008.29 when SA content = 10 % protein content (SPI-SA3-DX). The nanometer gel based on SPI-SA3-DX had the maximum turbidity and clear transparent solution without precipitation. Its particle size and polymer dispersibility index (PDI) were also the smallest, with values of (106.87 ± 4.51) nm and 0.21 ± 0.009, respectively. Transmission electron microscopy showed that nanogels had subspherical shell-core structures. Nanogels were stable under different pH, ionic strength, high temperature, and storage conditions.

Removal of cationic and anionic dyes from waste water in five seconds by a facile synthesis of a covalent organic polymer

Discharge of organic dyes from various industries into water bodies have polluted the resources appallingly which made them unsafe to use. Various materials developed for the removal of these dyes often lacks from cost effectiveness, good removal capacity and fast kinetics. On account of the imperative need for a cost-effective and efficient system for this purpose, we have developed a facile approach for the synthesis of Covalent Organic Polymer (COP) in a two-step strategy by incorporating a versatile functional group dithiocarbamate. This dithiocarbamate-based covalent organic polymer (D-COP) could remove multiple dyes (both cationic and anionic) simultaneously within a flash time with high uptake capacity. Out of five dyes, Eriochrome black T was removed with exceptional uptake capacity of > 4000 mg/g triumphing the existing reports followed by Congo red (1013 mg/g). On top of that, the removal was ultrafast, within 5 s with pseudo-second-order rate constant value 156.25 g/mg.min which is the highest ever reported. The selective adsorption of these dyes over methylene blue and Rhodamine B make D-COP applicable for the separation and purification of these dyes from the mixture. The material was also completely recycled and reused up to several cycles without hampering the performance under different pH, and ionic strength conditions too. The ultrafast and high removal efficiency even in real water samples makes the material more competent. This material, being efficient in terms of low-cost synthesis, removal efficiency, kinetics, and regeneration capability, can be further employed for higher scale water treatment applications.

Different electrostatic forces drive the binding kinetics of SARS-CoV, SARS-CoV-2 and MERS-CoV Envelope proteins with the PDZ2 domain of ZO1

The Envelope protein (E) is a structural protein encoded by the genome of SARS-CoV, SARS-CoV-2 and MERS-CoV Coronaviruses. It is poorly present in the virus but highly expressed in the host cell, with prominent role in virus assembly and virulence. The E protein possesses a PDZ-binding motif (PBM) at its C terminus that allows it to interact with host PDZ domain containing proteins. ZO1 is a key protein in assembling the cytoplasmic plaque of epithelial and endothelial Tight Junctions (TJs) as well as in determining cell differentiation, proliferation and polarity. The PDZ2 domain of ZO1 is known to interact with the Coronaviruses Envelope proteins, however the molecular details of such interaction have not been established. In this paper we directly measured, through Fluorescence Resonance Energy Transfer and Stopped-Flow methodology, the binding kinetics of the PDZ2 domain of ZO1 with peptides mimicking the C-terminal portion of the Envelope protein from SARS-CoV, SARS-CoV-2 and MERS-CoV in different ionic strength conditions. Interestingly, the peptide mimicking the E protein from MERS-CoV display much higher microscopic association rate constant with PDZ2 compared to SARS-CoV and SARS-CoV-2 suggesting a stronger contribution of electrostatic forces in the early events of binding. A comparison of thermodynamic and kinetic data obtained at increasing ionic strengths put in evidence different contribution of electrostatics in the recognition and complex formation events for the three peptides. Our data are discussed under the light of available structural data of PDZ2 domain of ZO1 and of previous works about these protein systems.

Co-transport of polystyrene microplastics and kaolinite colloids in goethite-coated quartz sand: Joint effects of heteropolymerization and surface charge modification

This study investigated the transport behavior of polystyrene microplastics (MPs) in saturated quartz sand and goethite-coated sand in the presence of coexisting kaolinite colloids. Column experiments were conducted under a wide range of solution chemistry conditions, including pH levels of 6.0, 7.0, and 9.0, as well as background Na+ concentrations of 5 mM and 25 mM. We found that: (1) The individual transport of MPs in porous media diminished both with increasing background ion strength and decreasing pH, and its transport ability was significantly dominated by the interactions between MPs and porous media rather than the interplay between MPs, which has been further corroborated by the aggregation stability experiments of MPs particles. (2) MPs had a much lower ability to move through goethite-coated sand columns than quartz sand columns. This is because goethite coating reduces the repulsion energy barriers between porous media and MPs. The increased specific surface area and surface complexity of sand columns after goethite coating should also account for this difference. (3) MPs transport would be subjected to the differentiated impact of co-transported kaolinite colloids in the two types of porous media. The promotion effect of kaolinite colloid on MPs' transport capacity is not significantly affected by background ionic strength changes when quartz sand is served as the porous medium; however, the promotion effect is highly correlated with the background ionic strength when goethite-coated sand is served as the porous medium. In comparison with low background ionic strength conditions, kaolinite colloids under high background ionic strength conditions significantly facilitated MPs transport. This is mainly because under high background ionic conditions, kaolinite colloids are more likely to be deposited on the surface of goethite-covered sand, competing with MPs for the limited deposition sites. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory is applicable to describe the transport behavior of MPs.

Ionic Strength Enhances the Multiphase Oxidation Rate of Sulfur Dioxide by Ozone in Aqueous Aerosols: Implications for Sulfate Production in the Marine Atmosphere.

Multiphase oxidation of sulfur dioxide (SO2) by ozone (O3) in alkaline sea salt aerosols is an important source of sulfate aerosols in the marine atmosphere. However, a recently reported low pH of fresh supermicron sea spray aerosols (mainly sea salt) would argue against the importance of this mechanism. Here, we investigated the impact of ionic strength on the kinetics of multiphase oxidation of SO2 by O3 in proxies of aqueous acidified sea salt aerosols with buffered pH of ∼4.0 via well-controlled flow tube experiments. We find that the sulfate formation rate for the O3 oxidation pathway proceeds 7.9 to 233 times faster under high ionic strength conditions of 2-14 mol kg-1 compared to the dilute bulk solutions. The ionic strength effect is likely to sustain the importance of multiphase oxidation of SO2 by O3 in sea salt aerosols in the marine atmosphere. Our results indicate that atmospheric models should consider the ionic strength effects on the multiphase oxidation of SO2 by O3 in sea salt aerosols to improve the predictions of the sulfate formation rate and the sulfate aerosol budget in the marine atmosphere.

Removal of Ciprofloxacin from Water by a Potassium Carbonate-Activated Sycamore Floc-Based Carbonaceous Adsorbent: Adsorption Behavior and Mechanism.

In this study, a porous carbonaceous adsorbent was prepared from sycamore flocs by pyrolysis method and K2CO3 activation. The effects of preparative conditions of the material on its adsorptive property were explored. The optimal material (SFB2-900) was obtained with a K2CO3/biochar mass ratio of 2:1 at an activation temperature of 900 °C, possessing a huge surface specific area (1651.27 m2/g). The largest adsorption capacity for ciprofloxacin on SFB2-900 was up to 430.25 mg/g. The adsorption behavior was well described by the pseudo-second-order kinetic model and the Langmuir isothermal model. Meanwhile, this process was spontaneous and exothermic. The obtained material showed excellent adsorption performance in the conditions of diverse pH range, ionic strength, and water quality of the solution. The optimum adsorption conditions (pH = 7.01, dosage = 0.6 g/L, and C0 = 52.94 mg/L) determined based on the response surface methodology were in accordance with the practical validation consequences. The good regeneration effect of SFB2-900 manifested that this material had great practical application potential. Combining the experimental results and density functional theory calculation results, the adsorption mechanisms mainly included pore filling, π-π EDA interactions, electrostatic interactions, and H-bonds. The material could be regarded as a novel and high-efficiency adsorbent for antibiotics. Additionally, these findings also provide reference for the reuse of waste biomass in water treatment.

Ionic strength modulates excision of uracil by SMUG1 from nucleosome core particles

Ionic strength affects many cellular processes including the packaging of genetic material in eukaryotes. For example, chromatin fibers are compacted in high ionic strength environments as are the minimal unit of packaging in chromatin, nucleosome core particles (NCPs). Furthermore, ionic strength is known to modulate several aspects of NCP dynamics including transient unwrapping of DNA from the histone protein core, nucleosome gaping, and intra- and internucleosomal interactions of the N-terminal histone tails. Changes in NCP structure may also impact interactions of transcriptional, repair, and other cellular machinery with nucleosomal DNA. One repair process, base excision repair (BER), is impacted by NCP structure and may be further influenced by changes in ionic strength. Here we examine the effects of ionic strength on the initiation of BER using biochemical assays. Using a population of NCPs containing uracil (U) at dozens of geometric locations, excision of U by single-strand selective monofunctional uracil DNA glycosylase (SMUG1) is assessed at higher and lower ionic strengths. SMUG1 has increased excision activity in the lower ionic strength conditions. On duplex DNA, however, SMUG1 activity is largely unaffected by ionic strength except at short incubation times, suggesting that changes in SMUG1 activity are likely due to alterations in NCP structure and dynamics. These results allow us to further understand the cellular role of SMUG1 in a changing ionic environment and broadly contribute to the understanding of BER on chromatin and genomic stability.

From speciation study to removal of Pb2+ from natural waters by a carnosine-based polyacrylamide/azlactone copolymer

A deep speciation study on L-carnosine (CAR) and Pb2+ system was performed in aqueous solution with the aim to assess its potential use as a sequestering agent of metal cation. To determine the best conditions for Pb2+ complexation, potentiometric measurements were carried out over a wide range of ionic strength (0.15 ≤ I/≤ 1 mol/L) and temperature (15 ≤ T/°C ≤ 37), and thermodynamic interaction parameters (logβ, ΔH, ΔG and TΔS) were determined. The speciation studies allowed us to simulate sequestration ability of CAR toward Pb2+ under different conditions of pH, ionic strength and temperature and to establish a priori the conditions for the best removal performance, i.e., pH > 7 and I = 001 mol/L. This preliminary investigation was very useful in optimizing removal procedures and limiting subsequent experimental measurements for adsorption tests. Therefore, to exploit the binding ability of CAR for Pb2+ removal from aqueous solutions, CAR was covalently grafted on an azlactone-activated beaded-polyacrylamide resin (AZ) using an efficient click coupling reaction (78.3% of coupling efficiency). The carnosine-based resin (AZCAR) was analyzed by ThermoGravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Differential Thermal Analysis (DTA). Morphology, surface area and pore size distribution were studied through a combination of Scanning Electron Microscope (SEM) and adsorption/desorption of N2 analyses according to the Brunauer-Emmett-Teller (BET) and Barret-Johner-Halenda (BJH) approaches. The adsorption capacity of AZCAR toward Pb2+ was investigated under conditions simulating the ionic strength and pH of different natural waters. The time needed to reach equilibrium in the adsorption process was 24 h, and the best performance was obtained at pH > 7, typical of most natural waters, with removal efficiency ranging from 90.8% (at I = 0.7 mol/L) to 99.0 (at I = 0.001 mol/L).

Significance of MnO2 Type and Solution Parameters in Manganese Removal from Water Solution.

A very low concentration of manganese (Mn) in water is a critical issue for municipal and industrial water supply systems. Mn removal technology is based on the use of manganese oxides (MnOx), especially manganese dioxide (MnO2) polymorphs, under different conditions of pH and ionic strength (water salinity). The statistical significance of the impact of polymorph type (akhtenskite ε-MnO2, birnessite δ-MnO2, cryptomelane α-MnO2 and pyrolusite β-MnO2), pH (2-9) and ionic strength (1-50 mmol/L) of solution on the adsorption level of Mn was investigated. The analysis of variance and the non-parametric Kruskal-Wallis H test were applied. Before and after Mn adsorption, the tested polymorphs were characterized using X-ray diffraction, scanning electron microscope techniques and gas porosimetry analysis. Here we demonstrated the significant differences in adsorption level between MnO2 polymorphs' type and pH; however, the statistical analysis proves that the type of MnO2 has a four times stronger influence. There was no statistical significance for the ionic strength parameter. We showed that the high adsorption of Mn on the poorly crystalline polymorphs leads to the blockage of micropores in akhtenskite and, contrary, causes the development of the surface structure of birnessite. At the same time, no changes in the surfaces of cryptomelane and pyrolusite, the highly crystalline polymorphs, were found due to the very small loading by the adsorbate.

Adsorptive removal of dichlorophenoxyacetic acid (2,4-D) using novel nanoparticles based on cationic surfactant-coated titania nanoparticles.

A novel nanomaterial based on cationic surfactant-coated TiO2 nanoparticle (CCTN) was systematically fabricated in this work. Synthesized titania nanoparticles were thoroughly characterized by XRD, FT-IR, HR-TEM, TEM-EDX, SEM with EDX mapping, BET, and ζ potential measurements. The adsorption of cationic surfactant, cetyltrimethylammonium bromide (CTAB), on TiO2 was studied under various pH and ionic strength conditions. Adsorption of CTAB on TiO2 increased with ionic strength increment in the presence of hemimicelle monolayer structure, indicating that nonelectrostatic and electrostatic forces control CTAB uptake. CTAB adsorption isotherms on TiO2 were according to a two-step model. Potential application in pesticide removal of 2,4-dichorophenoxy acetic acid (2,4-D) using CCTN was also studied. Optimum parameters for 2,4-D treatment through adsorption technique were pH 5, adsorption time of 120min, and CCTN dosage of 10mg·mL-1. Very low 2,4-D removal efficiency using TiO2 without CTAB coating was found to be approximately 28.5% whereas the removal efficiency was up to about 90% by using CCTN under optimum conditions, and the maximum adsorption capacity of 12.79mg·g-1 was found. Adsorption isotherms of 2,4-D on CCTN were more suitable with the Langmuir model than Freundlich. Adsorption mechanisms of 2,4-D on CCTN were mainly governed by Columbic attraction based on isotherms and surface charge changes.

Recrystallization Mediates the Gelation of Amorphous Drugs: The Case of Acemetacin

Amorphization is widely used as an effective method of increasing the solubility of insoluble drugs. However, some amorphous drugs exhibit a much lower dissolution rate than their corresponding crystalline form due to their gelation. In this study, we reported the gels formed from amorphous acemetacin (ACM) for the first time. Gelation was promoted at conditions of lower pH, higher temperature and lower ionic strength. Solid-state characterizations suggested that ACM gels may be formed by recrystallization. This mechanism provides a new direction in facilitating the elimination of gelation for amorphous drugs. Moreover, it also provides the basis for the development of sustained-release formulations using the gelation properties.

Stress-independent delay time in yielding of dilute colloidal gels.

We investigate the yielding under shear for dilute poly(N-isopropyl acrylamide-co-fumaric acid) (PNIPAM-FAc) colloidal gels obtained above the volume phase transition temperature. In this temperature range, the microgel suspensions form colloidal gels due to hydrophobic interparticle interactions under appropriate pH and ionic strength conditions. Step-strain tests revealed that yielding occurs when the applied strain exceeds a specific threshold, requiring a finite, stress-independent delay time (tD). This is distinct from previous findings on delayed yielding in other colloidal gels, where tD decreases with increasing stress. In the start-up shear tests, yield strain (γy) at a higher strain rate () increases with escalating , while γy at lower  remains constant. This characteristic γy- relationship is successfully explained by a simple model using the stress-independent tD value without an adjustable fitting parameter. The distinctive yielding behavior, underscored by a stress-independent tD, is expected to originate from strain-induced macroscopic phase separation into a dense colloidal gel and water, observable separately from rheological measurements.

Nanofluidic diodes based on asymmetric bio-inspired surface coatings in straight glass nanochannels.

In this study, we present nanofluidic diodes fabricated from straight glass nanochannels and functionalized using bio-inspired polydopamine (PDA) and poly-L-lysine (PLL) coatings. The resulting PDA coatings are shown to be asymmetric due to a combination of transport considerations which can be leveraged to provide a measure of control over the effective channel geometry. By subsequently introducing a layer of amine-bearing PLL chains covalently bound to the PDA, we enhance heterogeneities in the charge and ion distributions within the channel and enable significant current rectification between forward-bias and reverse-bias modes; our PDA-PLL-coated channels yielded a rectification ratio greater than 1000 in a 100 nm channel filled with 0.01× phosphate-buffered saline solution (PBS). We further demonstrated that at higher ionic strength conditions, reducing the solution pH increased the number of protonated amines within the PLL layer, amplifying the charge disparities along the channel and leading to greater rectification. As nanofluidic diodes with bipolar surface charge distributions tend to provide superior performance compared to those with a single wall charge polarity, we imposed a more bipolar charge distribution in our devices by partially coating our PDA-PLL-coated channels with negatively charged polyacrylic acid (PAA). These enhanced bipolar channels exhibited greater current rectification than the PDA-PLL-coated channels, reaching rectification ratios in excess of 100 even in more physiologically-relevant 1× PBS solutions. Our fabrication approach and the results herein provide a promising platform from which the scientific community can build upon in the relentless endeavor for improved sensitivity in biosensors and other analytical devices.