High Ion Affinity Research Articles

Coordinated self-assembly of ultraporous 3D aramid nanofibrous separators with a poly(vinyl alcohol) sheath for lithium-metal batteries

Li-metal batteries with a low negative/positive electrode capacity ratio require significant improvement to ensure their practical implementation as high-energy-density batteries. In the present study, ultraporous aramid nanofiber (ANF) separators with a poly(vinyl alcohol) (PVA) sheath were fabricated using a coordinated self-assembly process to produce an ultrahigh bulk (>95 %) and surface (>48.6 %) porosity and a high ion affinity. In this process, sol films consisting of an optimized mixture of aramid nanoseed sols and PVA were sequentially immersed in ethanol and water to induce the formation of a 3D aramid network and the phase separation of PVA by their rate differences, followed by swelling-induced pore formation. The resulting separators exhibited an excellent ion conductivity and Li+ ion transference number of up to 2.73 mS cm−1 and 0.78, respectively, with the effective suppression of Li dendritic growth and the formation of a stable fluorine-rich solid electrolyte interphase (SEI) layer on the Li-metal surface. Li/Li half cells exhibited stable operation for up to 1500 cycles with a high current density of 10 mA cm–2 and an areal capacity of 1 mAh cm–2, with Li/Cu half cells operating for over 244 cycles even with a lithiophobic Cu current collector. LFP/Li full cells with a low N/P ratio (∼2.03) exhibited stable operation for 172 cycles with an average Coulombic efficiency of 99.6 %. NCM/Li full cell with extremely low N/P ratio (0.96) and lean electrolyte condition (4 g Ah–1) stably operated for 55 cycles with projected energy density of 350.7 Wh kg–1.

Hydrothermal synthesis of hydroxy sodalite from fly ash for the removal of lead ions from water

Zeolites are known to possess valuable physiochemical properties such as adsorption, cation exchange, molecular sieving, and catalysis. In addition, zeolites are highly selective scavengers of a variety of heavy metals from liquid effluents through the process of ion exchange. The present study was performed to hydrothermally synthesize Na8[AlSiO4]6(OH)2·2H2O (also known as hydroxy sodalite hydrate). Due to its small aperture size, this material can be an ideal candidate for the separation of small molecules and ions from aquatic and gas mixtures. Synthetic zeolites offer many advantages over natural zeolites, such as higher ion affinity and adsorption capacity. Batch adsorption isotherm studies were conducted to evaluate the obtained adsorbent for the lead ion removal from aqueous media. Modeling lead ion adsorption using Langmuir and Freundlich isotherm expressions determined the capacity of the adsorbent. A removal efficiency of 98.1 % in a 3.0 g/l adsorbent/solution mixture with a maximum adsorption capacity of 153.8 mg/g was obtained. One potential application of the synthesized zeolite is for the lead removal in point-of-use treatment devices.

Structuring of H1 histone. Evidence of high-affinity binding sites for phosphate ions

Circular dichroism studies show that low concentrations of phosphate ions induce folding of the H1 histones. Sulfate and perchlorate anions have effects similar to phosphate indicating the presence on H1 histones of binding sites with high affinity for ions with tetrahedral geometry. In fact, the structuring efficiency of different ions, as determined by the midpoint value of the effect/concentration curve, is 0.05 M for NaCl, 0.005 M for NaClO4, 0.001 M for sodium phosphate and 0.0003 M for sodium sulfate on H1 histone from Chaetopterus variopedatus sperm chromatin. Phosphate shows similar folding efficiency also on calf thymus and on sea-urchin sperm H1 histones. The effect of phosphate ions on the H1 molecule is observed also by differential absorption spectroscopy in the region of absorption of amino acid side-chains. Binding studies by gel filtration chromatography on Sephadex columns show that phosphate binding occurs in the presence of structuring concentrations of sodium chloride. About 9 ATP molecules bind to H1 histones derived from non-active cell chromatins while only 3.5 ATP molecules bind to H1 derived from active somatic chromatins. The fluorescence of the tyrosine residues of Chaetopterus sperm H1 is enhanced by chloride ions and heavily quenched by phosphate ions in correlation with structuring of the molecule, demonstrating direct interactions between tyrosine residues and phosphate ions. The defined and limited number of phosphate groups bound per histone molecule, the high affinity of the interaction and the effect on the structure of the histone suggest the participation of phosphate groups in the binding of H1 histones to DNA.

An electrostatic model of a membrane ion pump.

The model is based upon an ion channel with an electric dipolar structure. With simplifying assumptions it is possible to calculate that a typical channel, 1 nm in diameter and 5 nm long, could contain at most two or three univalent cations at a time. The channel ion binding sites have an effective affinity for ions from the fluid bathing the negative end of the channel, several orders of magnitude higher than their affinity for ions from the fluid bathing the positive end of the channel. The approach of an external, positively charged body to the negative end of the channel, is sufficient to convert the two- or three-channel ion sites with high affinity for ions from the fluid bathing this end into very low affinity sites for the same ions that now have access only to the fluid bathing the other end of the channel. The change in affinity and fluid access requires no molecular or electrical change in the channel structure other than the passive superposition of the electrostatic potential of the dipolar channel and that of the charged body. An oscillating electric field externally applied to an electric dipolar channel is shown to result in the unidirectional pumping of cations in the direction of the channel dipole even against large adverse ion concentration gradients. The energy required must be supplied by the sources of the electric field. By using two such channels in close proximity, one selective for K+ ions with its dipole moment pointing into a cell and the other selective for Na+ ions with its dipole moment pointing out from the cell, it is possible to construct a model pump with calculated properties that simulate many of those measured for Na+-K+-ATPase, with both physiological and artificial ionic concentrations.