Veratridine Can Bind to a Site at the Mouth of the Channel Pore at Human Cardiac Sodium Channel NaV1.5

The cardiac sodium ion channel (NaV1.5) is a protein with four domains (DI-DIV), each with six transmembrane segments. Its opening and subsequent inactivation results in the brief rapid influx of Na+ ions resulting in the depolarization of cardiomyocytes. The neurotoxin veratridine (VTD) inhibits NaV1.5 inactivation resulting in longer channel opening times, and potentially fatal action potential prolongation. VTD is predicted to bind at the channel pore, but alternative binding sites have not been ruled out. To determine the binding site of VTD on NaV1.5, we performed docking calculations and high-throughput electrophysiology experiments. The docking calculations identified two distinct binding regions. The first site was in the pore, close to the binding site of NaV1.4 and NaV1.5 blocking drugs in experimental structures. The second site was at the “mouth” of the pore at the cytosolic side, partly solvent-exposed. Mutations at this site (L409, E417, and I1466) had large effects on VTD binding, while residues deeper in the pore had no effect, consistent with VTD binding at the mouth site. Overall, our results suggest a VTD binding site close to the cytoplasmic mouth of the channel pore. Binding at this alternative site might indicate an allosteric inactivation mechanism for VTD at NaV1.5.

High-Entropy-Stabilized Polyanionic Cathodes with Multiple Redox Reactions for Sodium-Ion Battery Applications

High-entropy (HE) materials containing multiple elements have created a growing interest in exploring the property limits of electrodes in energy storage and understanding the underlying chemical/physical mechanisms. Here, we show a substantial improvement in performance of HE-based cathodes in sodium-ion batteries (SIBs). Polyanionic structure has a large compositional flexibility and can incorporate many active transition-metal (TM) species, which is an ideal platform to design HE cathode materials. As a proof of concept, we show that HE sodium superionic conductor (HE-NASICON) materials can be synthesized via a facile sol-gel method. By comparing a group of HE-NASICON cathodes containing different contents of TM species, we demonstrate that the multi-Na-ions intercalation/deintercalation process is highly reversible, whereas capacity and cycling stability are improved. The HE-NASICON cathode with equal molarity of five TM species achieves a high capacity of 161 mA h g−1 and capacity retention of 85% when cycling at a high rate of 5 C over 1000 cycles. In-situ XRD and spherical-aberration-corrected transmission electron microscope (ACTEM) also demonstrate a robust trigonal phase with a volume change of merely 4.07% during the multi-Na-ions storage. These results reveal the effectiveness of HE concept in expediting high-performance polyanionic cathodes for real SIBs applications.

Investigating the properties and performance of 3A molecular sieves as an adsorbent to prevent coke formation in olefin dehydration process

To study the affinity of 3A aluminosilicate adsorbents to prevent oligomerization of olefin molecules and forming green oil, physical and chemical properties of 3A molecular sieves are measured by using characterization techniques such as temperature-programmed desorption (TPD), nitrogen (N2) and water adsorptions, X-ray diffraction (XRD), X-ray fluorescence (XRF), crushing strength, and carbon dioxide (CO2) adsorption. Moreover, coke formation affinities of the understudy adsorbents are evaluated in a bench-scale system using 1-butene and 1,3-butadiene at temperatures of 220 and 260 °C, and outcomes are validated against the actual data gathered from an industrial scale olefin dehydration plant. Results confirm that the type of binder and the amount of ion exchange affect the performance of a 3A molecular sieve nominated for dehydrating olefinic streams. The binder with the least amount of acidity is preferred, and at least 35% of Na ions of the 4A zeolite should be exchanged with K ions to make it applicable for synthesizing an appropriate 3A molecular sieve. Furthermore, to control the oligomerization and inhibit green oil formation, the CO2 adsorption and acidity of Trisiv shape molecular sieves with the sizes of 1/4 inch should be less than 0.5 wt % and 1.7 mmol NH3/g, respectively. For extrudate shape with the sizes of 1/16 inch CO2 adsorption and acidity should be less than 0.2 wt % and 2.2 mmol NH3/g, respectively.

The properties of highly concentrated aqueous CH3COOK/Na binary electrolyte and its use in sodium-ion batteries

Highly concentrated aqueous binary solutions of acetate salts are emerging as promising systems for advanced energy storage applications. Together with superior solubility of CH3COOK helpful in achieving water-in-salt electrolyte concentrations, the presence of CH3COOLi or CH3COONa permits intercalation of desired cations in electrode crystalline phases. Although these systems have captured profound scientific attention in recent years, a fundamental understanding of their physicochemical properties is still lacking. In this work, the thermal, rheological, transport, and electrochemical properties for a series of solutions comprising of 20 mol kg-1 of CH3COOK with different concentrations of CH3COONa are reported and discussed. The most concentrated solution, i.e., 20 mol kg-1 of CH3COOK with 7 mol kg-1 of CH3COONa came out to be the best in terms of a compromise between transport properties and electrochemical stability window. Such a solution has a conductivity of 21.2 mS cm-1 at 25°C and shows a stability window up to 3 V in “ideal” conditions, i.e., using small surface area and highly electrocatalytic electrode in a flooded cell. As a proof of concept of using this solution in sodium-ion batteries, carbon-coated LiTi2(PO4)3 (NASICON) demonstrated the ability to reversibly insert and de-insert Na+ ions at about -0.7 V vs. SHE with a first cycle anodic capacity of 85 mAh g-1, average charge efficiency of 96% at low current and a 90% capacity retention after 60 cycles. The very good kinetic properties of the interface are also demonstrated by the low value of activation energy for the charge transfer process (0.12 eV).

Fluorescent AgNCs Formed on Bifunctional DNA Template for Potassium Ion Detection

In this study, we examined properties of silver nanoclusters, which are AgNCs stabilized by DNA oligonucleotide scaffold containing G-quadruplex-forming sequences: human telomeric (Tel22) or thrombin-binding aptamer (TBA). Thus, we obtained two fluorescent probes abbreviated as Tel22C12-AgNCs and TBAC12-AgNCs, which were characterized using absorption, circular dichroism and fluorescence spectroscopy. Both probes emit green and red fluorescence. The presence of silver nanoclusters did not destabilize the formed G-quadruplexes. The structural changes of probes upon binding K+ or Na+ ions cause quenching in their red emission. Green emission was slightly quenched only in the case of Tel22C12-AgNCs; on the contrary, for TBAC12-AgNC’s green emission, we observed an increasing fluorescence signal. Moreover, the Tel22C12-AgNCs system shows not only a higher binding preference for K+ over Na+, but it was able to monitor small changes in K+ concentrations in the buffer mimicking extracellular conditions (high content of Na+ ions). These results suggest that Tel22C12-AgNCs exhibit the potential to monitor transmembrane potassium transport.

Cloning and Characterization of Two Putative P-Type ATPases from the Marine Microalga Dunaliella maritima Similar to Plant H+-ATPases and Their Gene Expression Analysis under Conditions of Hyperosmotic Salt Shock

The green microalga genus Dunaliella is mostly comprised of species that exhibit a wide range of salinity tolerance, including inhabitants of hyperhaline reservoirs. Na+ content in Dunaliella cells inhabiting saline environments is maintained at a fairly low level, comparable to that in the cells of freshwater organisms. However, despite a long history of studying the physiological and molecular mechanisms that ensure the ability of halotolerant Dunaliella species to survive at high concentrations of NaCl, the question of how Dunaliella cells remove excess Na+ ions entering from the environment is still debatable. For thermodynamic reasons it should be a primary active mechanism; for example, via a Na+-transporting ATPase, but the molecular identification of Na+-transporting mechanism in Dunaliella has not yet been carried out. Formerly, in the euryhaline alga D. maritima, we functionally identified Na+-transporting P-type ATPase in experiments with plasma membrane (PM) vesicles which were isolated from this alga. Here we describe the cloning of two putative P-type ATPases from D. maritima, DmHA1 and DmHA2. Phylogenetic analysis showed that both ATPases belong to the clade of proton P-type ATPases, but the similarity between DmHA1 and DmHA2 is not high. The expression of DmHA1 and DmHA2 in D. maritima cells under hyperosmotic salt shock was studied by qRT-PCR. Expression of DmHA1 gene decreases and remains at a relatively low level during the response of D. maritima cells to hyperosmotic salt shock. In contrast, expression of DmHA2 increases under hyperosmotic salt shock. This indicates that DmHA2 is important for overcoming hyperosmotic salt stress by the algal cells and as an ATPase it is likely directly involved in transport of Na+ ions. We assume that it is the DmHA2 ATPase that represents the Na+-transporting ATPase.

Distinct roles of the Na+ binding sites in the allosteric coupling mechanism of the glutamate transporter homolog, GltPh.

Glutamate transporters carry out the concentrative uptake of glutamate by harnessing the ionic gradients present across cellular membranes. A central step in the transport mechanism is the coupled binding of Na+ and substrate. The sodium coupled Asp transporter, GltPh is an archaeal homolog of glutamate transporters that has been extensively used to probe the transport mechanism. Previous studies have shown that hairpin-2 (HP2) functions as the extracellular gate for the aspartate binding site and plays a key role in the coupled binding of sodium and aspartate to GltPh. The binding sites for three Na+ ions (Na1-3) have been identified in GltPh but the specific roles of the individual Na+ sites in the binding process has not been elucidated. In this study, we developed assays to probe Na+ binding to the Na1 and Na3 sites and to monitor the conformational switch in the NMDGT motif. We used these assays along with a fluorescence assay to monitor HP2 movement and EPR spectroscopy to show that Na+ binding to the Na3 site is required for the NMDGT conformational switch while Na+ binding to the Na1 site is responsible for the partial opening of HP2. Complete opening of HP2 requires the conformational switch of the NMDGT motif and therefore Na+ binding to both the Na1 and the Na3 sites. Based on our studies we also propose an alternate pathway for the coupled binding of Na+ and Asp.

The Role of Sulphonic and Phosphoric Pendant Groups on the Diffusion of Monovalent Ions in Polyelectrolyte Membranes: A Molecular Dynamics Study

Lithium-ion consumption has risen significantly in recent years due to its use in portable devices. Alternative sources of lithium, which include the recovery from brine using the sustainable and eco-friendly electrodialysis technology, has been explored. This technology, however, requires effective cation-exchange membranes that allow the selective permeation of lithium ions. In this study, we have investigated, via molecular dynamics simulations, the role of the two common charged groups, the sulfonic and the phosphoric groups, in promoting the adsorption of monovalent ions from brine comprising Li+, Na+, Mg2+, and Ca2+ ions. The analysis of the mean square displacement of the ions revealed that Li+ and Na+ ions exhibit superior diffusion behaviors within the polyelectrolyte system. The O-atoms of the charged groups bind strongly with the divalent ions (Mg2+ and Ca2+), which raises their diffusion energy barrier and consequently lowers their rate of permeation. In contrast, the monovalent ions exhibit weaker interactions, with Na+ being slightly above Li+, enabling the permeation of Li+ ions. The present study demonstrates the role of both charged groups in cation-exchange membranes in promoting the diffusion of Li+ and Na+ ions, and could serve as a guide for the design of effective membranes for the recovery of these ions from brine.