Influence of Metal Ions on Model Protoamphiphilic Vesicular Systems: Insights from Laboratory and Analogue Studies

Metal ions strongly affect the self-assembly and stability of membranes composed of prebiotically relevant amphiphiles (protoamphiphiles). Therefore, evaluating the behavior of such amphiphiles in the presence of ions is a crucial step towards assessing their potential as model protocell compartments. We have recently reported vesicle formation by N-acyl amino acids (NAAs), an interesting class of protoamphiphiles containing an amino acid linked to a fatty acid via an amide linkage. Herein, we explore the effect of ions on the self-assembly and stability of model N-oleoyl glycine (NOG)-based membranes. Microscopic analysis showed that the blended membranes of NOG and Glycerol 1-monooleate (GMO) were more stable than pure NOG vesicles, both in the presence of monovalent and divalent cations, with the overall vesicle stability being 100-fold higher in the presence of a monovalent cation. Furthermore, both pure NOG and NOG + GMO mixed systems were able to self-assemble into vesicles in natural water samples containing multiple ions that were collected from active hot spring sites. Our study reveals that several aspects of the metal ion stability of NAA-based membranes are comparable to those of fatty acid-based systems, while also confirming the robustness of compositionally heterogeneous membranes towards high metal ion concentrations. Pertinently, the vesicle formation by NAA-based systems in terrestrial hot spring samples indicates the conduciveness of these low ionic strength freshwater systems for facilitating prebiotic membrane-assembly processes. This further highlights their potential to serve as a plausible niche for the emergence of cellular life on the early Earth.

Dysnatremias in Chronic Kidney Disease: Pathophysiology, Manifestations, and Treatment

The decreased ability of the kidney to regulate water and monovalent cation excretion predisposes patients with chronic kidney disease (CKD) to dysnatremias. In this report, we describe the clinical associations and methods of management of dysnatremias in this patient population by reviewing publications on hyponatremia and hypernatremia in patients with CKD not on dialysis, and those on maintenance hemodialysis or peritoneal dialysis. The prevalence of both hyponatremia and hypernatremia has been reported to be higher in patients with CKD than in the general population. Certain features of the studies analyzed, such as variation in the cut-off values of serum sodium concentration ([Na]) that define hyponatremia or hypernatremia, create comparison difficulties. Dysnatremias in patients with CKD are associated with adverse clinical conditions and mortality. Currently, investigation and treatment of dysnatremias in patients with CKD should follow clinical judgment and the guidelines for the general population. Whether azotemia allows different rates of correction of [Na] in patients with hyponatremic CKD and the methodology and outcomes of treatment of dysnatremias by renal replacement methods require further investigation. In conclusion, dysnatremias occur frequently and are associated with various comorbidities and mortality in patients with CKD. Knowledge gaps in their treatment and prevention call for further studies.

Slipknotted and unknotted monovalent cation-proton antiporters evolved from a common ancestor

While the slipknot topology in proteins has been known for over a decade, its evolutionary origin is still a mystery. We have identified a previously overlooked slipknot motif in a family of two-domain membrane transporters. Moreover, we found that these proteins are homologous to several families of unknotted membrane proteins. This allows us to directly investigate the evolution of the slipknot motif. Based on our comprehensive analysis of 17 distantly related protein families, we have found that slipknotted and unknotted proteins share a common structural motif. Furthermore, this motif is conserved on the sequential level as well. Our results suggest that, regardless of topology, the proteins we studied evolved from a common unknotted ancestor single domain protein. Our phylogenetic analysis suggests the presence of at least seven parallel evolutionary scenarios that led to the current diversity of proteins in question. The tools we have developed in the process can now be used to investigate the evolution of other repeated-domain proteins.

Application of counter-ion condensation in calculating the ion activity coefficients for interpreting the membrane selectivity

The transport selectivity of different cations through cation exchange membranes (CEMs) could be estimated with the partition coefficient (K_j^i) and the cation mobility ratio in the membrane ((u_m^i)⁄(u_m^j )), which in turn can be related to corresponding membrane conductivity and dimensional swelling degree data [Journal of Membrane Science, 2020, 597, 117645]. This method has been validated in two hydrocarbon-based CEMs, and the obtained K+/Na+ selectivity equals to the one obtained with conventional electrodialysis (ED) method. However, the K+/Na+ selectivity of perfluorosulfonic acid (PFSA) membranes, and the bi-/monovalent cation (Mg2+/Na+) selectivity of all three types of CEMs estimated with this ionic conductivity experimental approach deviate noticeably from corresponding values obtained with ED. In this work, it is proved that this deviation is mostly due to the simplification of cation activity coefficients in the membrane. Here, the cation activity coefficients in three types of CEMs are calculated according to Manning`s counter-ion condensation model. In this model, the Manning parameter (ξ) characterizing the dimensionless linear charge density is determined by the average distance between two adjacent fixed sulfonate groups (b) and the permittivity of hydrated membranes (ε). In hydrocarbon-based CEMs, the average distance between fixed sulfonate groups can be estimated by assuming homogeneous distribution of the fixed groups, while in PFSA membranes three representative structure models are employed to estimate this average distance. After accounting for the cation activity coefficients in the membrane, the cation transport selectivity obtained with the ionic conductivity experimental approach agrees well with the selectivity obtained with the ED method. This work shows the importance of cation activity coefficients in the membrane phase in interpreting the membrane transport properties, and complements the proposed conductivity approach to characterize the counter-ion selectivity of ion exchange membranes.

Significantly suppressing ion migration in metal halide perovskites via trace of multivalent interstitial doping

Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote performance and stability of perovskite optoelectronics. However, the interstitial doping accompanies inevitable lattice strain to impair long-range ordering and stability of the crystals to cause a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with significantly reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). Less but better, the prototypical perovskite solar cells incorporated with Nd3+ exhibits significantly enhanced photovoltaic performance and operational stability.

Specific Ion Effects on the Behavior of Mixtures of Sodium Iso-Butyl Xanthate and Sodium Diethyl Dithiophosphate during the Flotation of a Cu-Ni-PGM Ore: Effects of CaCl2 and NaCl

Inorganic electrolytes present in the process water used during froth flotation may have both beneficial and detrimental effects. These effects are said to be ion specific, as some ions may result in enhanced froth stability, increased mineral recoveries and decreased concentrate grades, while others may bring the opposite effects. Onsite process water quality variations have intensified the need to understand the relationship between inorganic electrolytes and flotation reagents on flotation performance. The use of mixtures of thiol collectors in sulfide flotation is a common practice across the globe; however, very few investigations have considered these in process waters of varying compositions. This study considers the effect of common cations, Na+ and Ca2+, in process water on the behavior of mixtures of thiol collectors. Single-salt solutions of NaCl and CaCl2 at an ionic strength of 0.0213 mol·dm−3 were used to investigate the behavior of mixtures of two thiol collectors. These were carefully selected to understand how mixtures of thiol collectors behave in the presence of a monovalent cation versus a polyvalent cation. Bench-scale froth flotation tests were conducted using a Cu-Ni-PGM ore from the Merensky Reef. The results have shown that the divalent cation, Ca2+, resulted in higher %Cu and %Ni recoveries at all collector mixtures compared to the monovalent cation, Na+. The concentrate grades were, however, slightly compromised, as slightly more gangue reported to the concentrate in the presence of Ca2+. This behavior is attributed to the effect of polyvalent cations on bubble coalescence and froth stability.