Project description:The high ion selectivity of potentiometric and optical sensors based on ionophore-based polymeric membranes is thermodynamically limited. Here, we report that the voltammetric selectivity of thin ionophore-based polymeric membranes can be kinetically improved by several orders of magnitude in comparison with their thermodynamic selectivity. The kinetic improvement of voltammetric selectivity is evaluated quantitatively by newly introducing a voltammetric selectivity coefficient in addition to a thermodynamic selectivity coefficient. Experimentally, both voltammetric and thermodynamic selectivity coefficients are determined from cyclic voltammograms of excess amounts of analyte and interfering ions with respect to the amount of a Na(+)- or Li(+)-selective ionophore in thin polymeric membranes. We reveal the slower ionophore-facilitated transfer of a smaller alkaline earth metal cation with higher hydrophilicity across the membrane/water interface, thereby kinetically improving voltammetric Na(+) selectivity against calcium, strontium, and barium ions by 3, 2, and 1 order of magnitude, respectively, in separate solutions. Remarkably, voltammetric Na(+) and Li(+) selectivity against calcium and magnesium ions in mixed solutions is improved by 4 and >7 orders of magnitude, respectively, owing to both thermodynamic and kinetic effects in comparison with thermodynamic selectivity in separate solutions. Advantageously, the simultaneous detection of sodium and calcium ions is enabled voltammetrically in contrast to the potentiometric and optical counterparts. Mechanistically, we propose a new hypothetical model that the slower transfer of a more hydrophilic ion is controlled by its partial dehydration during the formation of the adduct with a "water finger" prior to complexation with an ionophore at the membrane/water interface.
Project description:We report the first characterization study of commercial prototype carbon nanotube (CNT) membranes consisting of sub-1.27-nm-diameter CNTs traversing a large-area nonporous polysulfone film. The membranes show rejection of NaCl and MgSO4 at higher ionic strengths than have previously been reported in CNT membranes, and specific size selectivity for analytes with diameters below 1.24 nm. The CNTs used in the membranes were arc discharge nanotubes with inner diameters of 0.67 to 1.27 nm. Water flow through the membranes was 1000 times higher than predicted by Hagen-Poiseuille flow, in agreement with previous CNT membrane studies. Ideal gas selectivity was found to deviate significantly from that predicted by both viscous and Knudsen flow, suggesting that surface diffusion effects may begin to dominate gas selectivity at this size scale.
Project description:The great potential of nanoporous membranes for water filtration and chemical separation has been challenged by the trade-off between selectivity and permeability. Here we report on nanoporous polymer membranes with an excellent balance between selectivity and permeability of ions. Our membranes are fabricated by irradiating 2-?m-thick polyethylene terephthalate Lumirror® films with GeV heavy ions followed by ultraviolet exposure. These membranes show a high transport rate of K+ ions of up to 14?mol?h-1?m-2 and a selectivity of alkali metal ions over heavy metal ions of >500. Combining transport experiments and molecular dynamics simulations with a polymeric nanopore model, we demonstrate that the high permeability is attributable to the presence of nanopores with a radius of ~0.5?nm and a density of up to 5?×?1010?cm-2, and the selectivity is ascribed to the interaction between the partially dehydrated ions and the negatively charged nanopore wall.
Project description:Kiss-and-run exocytosis, consisting of reversible fusion between the vesicle membrane and the plasma membrane, is considered to lead to full fusion after stimulation of vesicles containing classical transmitters. However, whether this is also the case in the fusion of peptidergic vesicles is unknown. Previously, we have observed that spontaneous neuropeptide discharge from a single vesicle is slower than stimulated release, because of the kinetic constraints of fusion pore opening. To explore whether slow spontaneous release also reflects a relatively narrow fusion pore, we analyzed the permeation of FM 4-64 dye and HEPES molecules through spontaneously forming fusion pores in lactotroph vesicles expressing synaptopHluorin, a pH-dependent fluorescent fusion marker. Confocal imaging showed that half of the spontaneous exocytotic events exhibited fusion pore openings associated with a change in synaptopHluorin fluorescence but were impermeable to FM 4-64 and HEPES. Together with membrane capacitance measurements, these findings indicate an open fusion pore diameter <0.5 nm, much smaller than the neuropeptides. In stimulated cells, >70% of exocytotic events exhibited a larger, FM 4-64-permeable pore (>1 nm). Interestingly, capacitance measurements showed that the majority of exocytotic events in spontaneous and stimulated conditions were transient. Stimulation increased the frequency of transient events and the fusion pore dwell time but decreased the fraction of events with lowest measurable fusion pore. Kiss-and-run is the predominant mode of exocytosis in resting and in stimulated peptidergic vesicles. Stimulation prolongs the effective opening of the fusion pore and expands its primary subnanometer diameter to enable hormone secretion without full fusion.
Project description:Isotopes of heavier gases including carbon (13C/14C), nitrogen (13N), and oxygen (18O) are highly important because they can be substituted for naturally occurring atoms without significantly perturbing the biochemical properties of the radiolabelled parent molecules. These labelled molecules are employed in clinical radiopharmaceuticals, in studies of brain disease and as imaging probes for advanced medical imaging techniques such as positron-emission tomography (PET). Established distillation-based isotope gas separation methods have a separation factor (S) below 1.05 and incur very high operating costs due to high energy consumption and long processing times, highlighting the need for new separation technologies. Here, we show a rapid and highly selective adsorption-based separation of 18O2 from 16O2 with S above 60 using nanoporous adsorbents operating near the boiling point of methane (112 K), which is accessible through cryogenic liquefied-natural-gas technology. A collective-nuclear-quantum effect difference between the ordered 18O2 and 16O2 molecular assemblies confined in subnanometer pores can explain the observed equilibrium separation and is applicable to other isotopic gases.
Project description:State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu2+, Ni2+, Zn2+, Co2+, and Mg2+. We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.
Project description:The phospholipid bilayer has evolved to be a protective and selective barrier by which the cell maintains high concentrations of life sustaining organic and inorganic material. As gatekeepers responsible for an immense amount of bidirectional chemical traffic between the cytoplasm and extracellular milieu, ion channels have been studied in detail since their postulated existence nearly three-quarters of a century ago. Over the past fifteen years, we have begun to understand how selective permeability can be achieved for both cationic and anionic ions. Our mechanistic knowledge has expanded recently with studies of a large family of anion channels, the Formate Nitrite Transport (FNT) family. This family has proven amenable to structural studies at a resolution high enough to reveal intimate details of ion selectivity and gating. With five representative members having yielded a total of 15 crystal structures, this family represents one of the richest sources of structural information for anion channels.
Project description:Ion channels play a key role in regulating cell behavior and in electrical signaling. In these settings, polar and charged functional groups, as well as protein response, compensate for dehydration in an ion-dependent way, giving rise to the ion selective transport critical to the operation of cells. Dehydration, though, yields ion-dependent free-energy barriers and thus is predicted to give rise to selectivity by itself. However, these barriers are typically so large that they will suppress the ion currents to undetectable levels. Here, we establish that graphene displays a measurable dehydration-only mechanism for selectivity of K+ over Cl-. This fundamental mechanism, one that depends only on the geometry and hydration, is the starting point for selectivity for all channels and pores. Moreover, while we study selectivity of K+ over Cl- we find that dehydration-based selectivity functions for all ions, that is, cation over cation selectivity (e.g., K+ over Na+). Its likely detection in graphene pores resolves conflicting experimental results, as well as presents a new paradigm for characterizing the operation of ion channels and engineering molecular/ionic selectivity in filtration and other applications.
Project description:Ion transport in nanoconfinement exhibits significant features such as ionic rectification, ionic selectivity, and ionic gating properties, leading to the potential applications in desalination, water treatment, and energy conversion. Two-dimensional nanofluidics provide platforms to utilize this phenomenon for capturing osmotic energy. However, it is challenging to further improve the power output with inadequate charge density. Here we demonstrate a feasible strategy by employing Kevlar nanofiber as space charge donor and cross-linker to fabricate graphene oxide composite membranes. The coupling of space charge and surface charge, enabled by the stabilization of interlayer spacing, plays a key role in realizing high ion selectivity and the derived high-performance osmotic power conversion up to 5.06 W/m2. Furthermore, the output voltage of an ensemble of the membranes in series could reach 1.61 V, which can power electronic devices. The system contributes a further step toward the application of energy conversion.
Project description:State-of-the-art desalination membranes exhibit high water-salt selectivity, but their ability to discriminate between ions is limited. Elucidating the fundamental mechanisms underlying ion transport and selectivity in subnanometer pores is therefore imperative for the development of ion-selective membranes. Here, we compare the overall energy barrier for salt transport and energy barriers for individual ion transport, showing that cations and anions traverse the membrane pore in an independent manner. Supported by density functional theory simulations, we demonstrate that electrostatic interactions between permeating counterion and fixed charges on the membrane substantially hinder intrapore diffusion. Furthermore, using quartz crystal microbalance, we break down the contributions of partitioning at the pore mouth and intrapore diffusion to the overall energy barrier for salt transport. Overall, our results indicate that intrapore diffusion governs salt transport through subnanometer pores due to ion-pore wall interactions, providing the scientific base for the design of membranes with high ion-ion selectivity.