Counterion Distribution in the Stern Layer on Charged Surfaces.

Counterion adsorption at the solid-liquid interface affects numerous applications. However, the counterion adsorption density in the Stern layer has remained poorly evaluated. Here we report the direct determination of surface charge density at the shear plane between the Stern layer and the diffuse layer. By the Grahame equation extension and streaming current measurements for different solid surfaces in different aqueous electrolytes, we are able to obtain the counterion adsorption density in the Stern layer, which is mainly related to the surface charge density but is less affected by the bulk ion concentration. The charge inversion concentration is further found to be sensitive to the ion type and ion valence rather than to the charged surface, which is attributed to the ionic competitive adsorption and ion-ion correlations. Our findings offer a framework for understanding ion distribution in many physical and chemical processes where the Stern layer is ubiquitous.

Perfluorinated Amines: Accelerating Lithium Electrodeposition by Tailoring Interfacial Structure and Modulated Solvation for High-Performance Batteries.

Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li+ and enhance the migration of Li+. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.

Fabrication and stability of W/O/W emulsions stabilized by gum arabic and polyglycerol polyricinoleate.

BACKGROUND: In order to study the effect of adsorption of surfactant at the two interfacial layers on emulsion stability, the kinetically stable water-in-oil-in-water (W/O/W) emulsion carriers were prepared using polyglycerol polyricinoleate (PGPR) and gum arabic (GA) as emulsifiers. The relationship between the adsorption of the surfactant and the stability mechanism of the emulsions was elucidated. RESULTS: When the contents of PGPR and GA were low, the interfaces between oil and the inner and outer water phases, respectively, could not be completely covered. However, when the concentration of PGPR was higher than 60 g kg-1 , the excess PGPR was adsorbed on the interface between the oil phase and the outer water phase. When the concentration of GA reached 80 g kg-1 , more GA was adsorbed to the oil-in-water interface. Moreover, the presence of PGPR on the interface could reduce the adsorption capacity of GA. Two types of kinetically stable emulsions were obtained by optimizing the interface composition (60 g kg-1 GA/80 g kg-1 PGPR and 60 g kg-1 PGPR/80 g kg-1 GA). The kinetically stable W/O/W emulsions prepared in this study were successfully used to encapsulate a hydrophilic vitamin (vitamin B12) with an encapsulation efficiency (EE) of 80% and release efficiency (RE) of 95%. The interfacial adsorption GA can accelerate the hydrolysis of fat. CONCLUSION: Overall, this study provides a new strategy for the preparation of W/O/W emulsions, which might be beneficial for application in food, cosmetic, chemical, and pharmaceutical industries. © 2023 Society of Chemical Industry.

Competitive Adsorption of a Monoclonal Antibody and Nonionic Surfactant at the PDMS/Water Interface.

Interfacial adsorption of monoclonal antibodies (mAbs) can cause structural deformation and induce undesired aggregation and precipitation. Nonionic surfactants are often added to reduce interfacial adsorption of mAbs which may occur during manufacturing, storage, and/or administration. As mAbs are commonly manufactured into ready-to-use syringes coated with silicone oil to improve lubrication, it is important to understand how an mAb, nonionic surfactant, and silicone oil interact at the oil/water interface. In this work, we have coated a polydimethylsiloxane (PDMS) nanofilm onto an optically flat silicon substrate to facilitate the measurements of adsorption of a model mAb, COE-3, and a commercial nonionic surfactant, polysorbate 80 (PS-80), at the siliconized PDMS/water interface using spectroscopic ellipsometry and neutron reflection. Compared to the uncoated SiO2 surface (mimicking glass), COE-3 adsorption to the PDMS surface was substantially reduced, and the adsorbed layer was characterized by the dense but thin inner layer of 16 Å and an outer diffuse layer of 20 Å, indicating structural deformation. When PS-80 was exposed to the pre-adsorbed COE-3 surface, it removed 60 wt % of COE-3 and formed a co-adsorbed layer with a similar total thickness of 36 Å. When PS-80 was injected first or as a mixture with COE-3, it completely prevented COE-3 adsorption. These findings reveal the hydrophobic nature of the PDMS surface and confirm the inhibitory role of the nonionic surfactant in preventing COE-3 adsorption at the PDMS/water interface.

Investigating the Orientation of an Interfacially Adsorbed Monoclonal Antibody and Its Fragments Using Neutron Reflection.

Interfacial adsorption is a molecular process occurring during the production, purification, transport, and storage of antibodies, with a direct impact on their structural stability and subsequent implications on their bioactivities. While the average conformational orientation of an adsorbed protein can be readily determined, its associated structures are more complex to characterize. Neutron reflection has been used in this work to investigate the conformational orientations of the monoclonal antibody COE-3 and its Fab and Fc fragments at the oil/water and air/water interfaces. Rigid body rotation modeling was found to be suitable for globular and relatively rigid proteins such as the Fab and Fc fragments but less so for relatively flexible proteins such as full COE-3. Fab and Fc fragments adopted a 'flat-on' orientation at the air/water interface, minimizing the thickness of the protein layer, but they adopted a substantially tilted orientation at the oil/water interface with increased layer thickness. In contrast, COE-3 was found to adsorb in tilted orientations at both interfaces, with one fragment protruding into the solution. This work demonstrates that rigid-body modeling can provide additional insights into protein layers at various interfaces relevant to bioprocess engineering.

Predicting Concentration- and Ionic-Strength-Dependent Air-Water Interfacial Partitioning Parameters of PFASs Using Quantitative Structure-Property Relationships (QSPRs).

Air-water interfacial retention of poly- and perfluoroalkyl substances (PFASs) is increasingly recognized as an important environmental process. Herein, column transport experiments were used to measure air-water interfacial partitioning values for several perfluoroalkyl ethers and for PFASs derived from aqueous film-forming foam, while batch experiments were used to determine equilibrium Kia data for compounds exhibiting evidence of rate-limited partitioning. Experimental results suggest a Freundlich isotherm best describes PFAS air-water partitioning at environmentally relevant concentrations (101-106 ng/L). A multiparameter regression analysis for Kia prediction was performed for the 15 PFASs for which equilibrium Kia values were determined, assessing 246 possible combinations of 8 physicochemical and system properties. Quantitative structure-property relationships (QSPRs) based on three to four parameters provided predictions of high accuracy without model overparameterization. Two QSPRs (R2 values of 0.92 and 0.83) were developed using an assumed average Freundlich n value of 0.65 and validated across a range of relevant concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and hexafluoropropylene oxide-dimer acid (i.e., GenX). A mass action model was further modified to account for the changing ionic strength on PFAS air-water interfacial sorption. The final result was two distinct QSPRs for estimating PFAS air-water interfacial partitioning across a range of aqueous concentrations and ionic strengths.

Predicting Interfacial Tension and Adsorption at Fluid-Fluid Interfaces for Mixtures of PFAS and/or Hydrocarbon Surfactants.

Many per- and polyfluoroalkyl substances (PFAS) are surface-active and adsorb at fluid-fluid interfaces. The interfacial adsorption controls PFAS transport in multiple environmental systems, including leaching through soils, accumulation in aerosols, and treatment methods such as foam fractionation. Most PFAS contamination sites comprise mixtures of PFAS as well as hydrocarbon surfactants, which complicates their adsorption behaviors. We present a mathematical model for predicting interfacial tension and adsorption at fluid-fluid interfaces for multicomponent PFAS and hydrocarbon surfactants. The model is derived from simplifying a prior advanced thermodynamic-based model and applies to nonionic and ionic mixtures of the same charge sign with swamping electrolytes. The only required model inputs are the single-component Szyszkowski parameters obtained for the individual components. We validate the model using literature interfacial tension data of air-water and NAPL (non-aqueous phase liquid)-water interfaces covering a wide range of multicomponent PFAS and hydrocarbon surfactants. Application of the model to representative porewater PFAS concentrations in the vadose zone suggests competitive adsorption can significantly reduce PFAS retention (up to 7 times) at some highly contaminated sites. The multicomponent model can be readily incorporated into transport models to simulate the migration of mixtures of PFAS and/or hydrocarbon surfactants in the environment.

Investigation of interfacial adsorption between microplastics and methylparaben in aqueous solution.

Microplastics and parabens are considered to be a global contaminants, especially in the aquatic ecosystem. The interfacial interaction between four types of microplastics including polystyrene, polyethylene, polyethylene terephthalate, and polyvinyl chloride, and methylparaben were investigated in this study. The results showed that molecular layer dominates the adsorption, with the rate significantly affected by both internal diffusion and external diffusion. Among the four types, polystyrene and polyvinyl chloride showed the smallest and biggest adsorption capability, with the values were 0.656 and 1.269 mg g-1, respectively. For the adsorption capability, smaller particle size and higher pH value possessed positive effects. However, the existence of metal ions could inhibit the adsorption process, except for a weak promotion at low salinity. Physical adsorption effects, such as electrostatic interaction, hydrogen bond formation, and covalent bond formation, had been identified that dominated the adsorption. This finding could be served as a speculative foundation for the further study of the toxicity, migration, and ecological risk assessment of microplastics in aquatic ecosystem.

Unlocking the Interfacial Adsorption-Intercalation Pseudocapacitive Storage Limit to Enabling All-Climate, High Energy/Power Density and Durable Zn-Ion Batteries.

Sluggish storage kinetics and insufficient performance are the major challenges that restrict the transition metal dichalcogenides (TMDs) applied for zinc ion storage, especially at the extreme temperature conditions. Herein, a multiscale interface structure-integrated modulation concept was presented, to unlock the omnidirectional storage kinetics-enhanced porous VSe2-x ⋅n H2 O host. Theory research indicated that the co-modulation of H2 O intercalation and selenium vacancy enables enhancing the interfacial zinc ion capture ability and decreasing the zinc ion diffusion barrier. Moreover, an interfacial adsorption-intercalation pseudocapacitive storage mechanism was uncovered. Such cathode displayed remarkable storage performance at the wide temperature range (-40-60 °C) in aqueous and solid electrolytes. In particular, it can retain a high specific capacity of 173 mAh g-1 after 5000 cycles at 10 A g-1 , as well as a high energy density of 290 Wh kg-1 and a power density of 15.8 kW kg-1 at room temperature. Unexpectedly, a remarkably energy density of 465 Wh kg-1 and power density of 21.26 kW kg-1 at 60 °C also can be achieved, as well as 258 Wh kg-1 and 10.8 kW kg-1 at -20 °C. This work realizes a conceptual breakthrough for extending the interfacial storage limit of layered TMDs to construct all-climate high-performance Zn-ion batteries.

Influence of Residual Nonaqueous-Phase Liquids (NAPLs) on the Transport and Retention of Perfluoroalkyl Substances.

Per- and polyfluoralkyl substances (PFAS) are known to accumulate at interfaces, and the presence of nonaqueous-phase liquids (NAPLs) could influence the PFAS fate in the subsurface. Experimental and mathematical modeling studies were conducted to investigate the effect of a representative NAPL, tetrachloroethene (PCE), on the transport behavior of PFAS in a quartz sand. Perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA), a 1:1 mixture of PFOS and PFNA, and a mixture of six PFAS (PFOS, PFNA, perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS)) were used to assess PFAS interactions with PCE-NAPL. Batch studies indicated that PFAS partitioning into PCE-NAPL (Knw < 0.1) and adsorption on 60-80 mesh Ottawa sand (Kd < 6 × 10-5 L/g) were minimal. Column studies demonstrated that the presence of residual PCE-NAPL (∼16% saturation) delayed the breakthrough of PFOS and PFNA, with minimal effects on the mobility of PFBS, PFHpA, PFHxS, and PFOA. Breakthrough curves (BTCs) obtained for PFNA and PFOS alone and in mixtures were nearly identical, indicating the absence of competitive adsorption effects. A mathematical model that accounts for NAPL-water interfacial sorption accurately reproduced PFAS BTCs, providing a tool to predict PFAS fate and transport in co-contaminated subsurface environments.