Biomimetic Channels Design in Metal-Organic Framework Enabling Highly Lithium-Ion Conduction for Lithium-Metal Batteries.

Solid-state electrolytes (SSEs) based on metal-organic frameworks (MOFs) are an ideal material for constructing high-performance lithium metal batteries (LMBs). However, the low ion conductivity and poor interface contact (especially at low temperatures) still seriously hinder its further application. Herein, inspired by the Na+/K+ conduction in biology systems, a series (NH2, OH, NH-(CH2)3-SO3H)-modified MIL-53-X as SSEs is reported. These functional groups are similar to anions suspended in biological ion channels, partially repelling anions while allowing cations to be effectively transported through pore channels. Subsequently, MIL-53-X with hierarchical pore structure (H-MIL-53-X) is obtained by introducing lauric acid as a regulator, and then the effects of structural design and morphology control on its performance are explored. The conductivity of H-MIL-53-NH-SO3Li with multi-level pore structure and modified by sulfonic acid groups reached 2.2 × 10-3 S cm-1 at 25 °C, lithium-ion transference number of 0.78. Besides, the H-MIL-53-NH-SO3Li still has an excellent conductivity of 10-4 S cm-1 at -40 °C. Additionally, LiFePO4/Li batteries equipped with H-MIL-53-NH-SO3Li SSEs could operate stably for over 200 cycles at 0.1 C. The strategy of combining structural and morphological design of MOFs with biomimetic ion channels opens new avenues for the design of high-performance SSEs.

A biomimetic ion channel shortens the QT interval of type 2 long QT syndrome through efficient transmembrane transport of potassium ions.

Potassium ion transport across myocardial cell membrane is essential for type 2 long QT syndrome (LQT2). However, the dysfunction of potassium ion transport due to genetic mutations limits the therapeutic effect in treating LQT2. Biomimetic ion channels that selectively and efficiently transport potassium ions across the cellular membranes are promising for the treatment of LQT2. To corroborate this, we synthesized a series of foldamer-based ion channels with different side chains, and found a biomimetic ion channel of K+ (BICK) with the highest transport activity among them. The selected BICK can restore potassium ion transport and increase transmembrane potassium ion current, thus shortening phase 3 of action potential (AP) repolarization and QT interval in LQT2. Moreover, BICK does not affect heart rate and cardiac rhythm in treating LQT2 model induced by E4031 in isolated heart as well as in guinea pigs. By restoring ion transmembrane transport tactic, biomimetic ion channels, such as BICK, will show great potential in treating diseases related to ion transport blockade. STATEMENT OF SIGNIFICANCE: Type 2 long QT syndrome (LQT2) is a disease caused by K+ transport disorder, which can cause malignant arrhythmia and even death. There is currently no radical cure, so it is critical to explore ways to improve K+ transmembrane transport. In this study, we report that a small-molecule biomimetic ion channel BICK can efficiently simulate natural K+ channel proteins on the cardiomyocyte and cure E4031-induced LQT2 in guinea pig by restoring K+ transport function for the first time. This study found that the potassium transmembrane transport by BICK significantly reduced the QT interval, which provides a conceptually new strategy for the treatment of LQT2 disease.

Hollow-Particles Quasi-Solid-State Electrolytes with Biomimetic Ion Channels for High-Performance Lithium-Metal Batteries.

Solid-state electrolytes (SSEs) are the core material of solid-state lithium metal batteries (SLMBs), which are being researched urgently owing to their high energy and safety. Both high ionic conductivity and excellent cycling stability remain the primary goal of solid-state electrolytes. Herein, inspired by K+ /Na+ ion channels in cell membrane of eukaryotes, a novel hollow UiO-66 with biomimetic ion channels based on quasi-solid-state electrolytes (QSSEs) is designed. The hollow UiO-66 spheres containing biomimetic ion channels can spontaneously combine anions and incorporate more lithium ions, creating improved ionic conductivity (1.15 × 10-3 S cm-1 ) and lithium-ion transference number (0.70) at room temperature. The long-term cycling of symmetric batteries and COMSOL simulations demonstrate that this biomimetic strategy enables uniform ion flux to suppress Li dendrites. Furthermore, the Li metal full cells paired with LiFePO4 cathode exhibit excellent cycling stability and rate performance. Consequently, the strategy of designing biomimetic QSSEs opens up a new path for developing high-performance electrolytes for SLMBs.

An Electrically Actuated, Carbon-Nanotube-Based Biomimetic Ion Pump.

Single-walled carbon nanotubes (SWCNTs) are well-established transporters of electronic current, electrolyte, and ions. In this work, we demonstrate an electrically actuated biomimetic ion pump by combining these electronic and nanofluidic transport capabilities within an individual SWCNT device. Ion pumping is driven by a solid-state electronic input, as Coulomb drag coupling transduces electrical energy from solid-state charge along the SWCNT shell to electrolyte inside the SWCNT core. Short-circuit ionic currents, measured without an electrolyte potential difference, exceed 1 nA and scale larger with increasing ion concentrations through 1 M, demonstrating applicability under physiological (∼140 mM) and saltwater (∼600 mM) conditions. The interlayer coupling allows ionic currents to be tuned with the source-drain potential difference and electronic currents to be tuned with the electrolyte potential difference. This combined electronic-nanofluidic SWCNT device presents intriguing applications as a biomimetic ion pump or component of an artificial membrane.

Biomimetic Nanotubes Based on Cyclodextrins for Ion-Channel Applications.

Biomimetic membrane channels offer a great potential for fundamental studies and applications. Here, we report the fabrication and characterization of short cyclodextrin nanotubes, their insertion into membranes, and cytotoxicity assay. Mass spectrometry and high-resolution transmission electron microscopy were used to confirm the synthesis pathway leading to the formation of short nanotubes and to describe their structural parameters in terms of length, diameter, and number of cyclodextrins. Our results show the control of the number of cyclodextrins threaded on the polyrotaxane leading to nanotube synthesis. Structural parameters obtained by electron microscopy are consistent with the distribution of the number of cyclodextrins evaluated by mass spectrometry from the initial polymer distribution. An electrophysiological study at single molecule level demonstrates the ion channel formation into lipid bilayers, and the energy penalty for the entry of ions into the confined nanotube. In the presence of nanotubes, the cell physiology is not altered.