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Conjugated microporous polymer membranes for light-gated ion transport.

ABSTRACT: Inspired by the light-gated ion channels in cell membranes that play important roles in many biological activities, herein, we developed an artificial light-gated ion channel membrane out of conjugated microporous polymers. Through bottom-up design of the monomer molecular structure and by the electropolymerization method, the membrane pore size and thickness were precisely controlled on the molecular level. The obtained membrane exhibited uniform pore size and highly sensitive light-switchable response. The photoisomerization of the polymer chain resulted in a reversible "on and off" light control over the pore size and subsequently led to light-gated ion transport across the membrane for a series of ions including hydrogen, potassium, sodium, lithium, calcium, magnesium, and aluminum ions.

SUBMITTER: Zhou Z

PROVIDER: S-EPMC9205585 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Electropolymerization of robust conjugated microporous polymer membranes for rapid solvent transport and narrow molecular sieving.

Project description:Pore size uniformity is one of the most critical parameters in determining membrane separation performance. Recently, a novel type of conjugated microporous polymers (CMPs) has shown uniform pore size and high porosity. However, their brittle nature has prevented them from preparing robust membranes. Inspired by the skin-core architecture of spider silk that offers both high strength and high ductility, herein we report an electropolymerization process to prepare a CMP membrane from a rigid carbazole monomer, 2,2',7,7'-tetra(carbazol-9-yl)-9,9'-spirobifluorene, inside a robust carbon nanotube scaffold. The obtained membranes showed superior mechanical strength and ductility, high surface area, and uniform pore size of approximately 1 nm. The superfast solvent transport and excellent molecular sieving well surpass the performance of most reported polymer membranes. Our method makes it possible to use rigid CMPs membranes in pressure-driven membrane processes, providing potential applications for this important category of polymer materials.

| S-EPMC7578036 | biostudies-literature

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

Project description:Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

| S-EPMC5445531 | biostudies-literature

A Conjugated Microporous Polymer for Palladium-Free, Visible Light-Promoted Photocatalytic Stille-Type Coupling Reactions.

Project description:The Stille coupling reaction is a versatile method to mainly form aromatic C-C bonds. However, up to now, the use of palladium catalysts is necessary. Here, a palladium-free and photocatalytic Stille-type coupling reaction of aryl iodides and aryl stannanes catalyzing a conjugated microporous polymer-based phototcatalyst under visible light irradiation at room temperature is reported. The novel coupling reaction mechanism occurs between the photogenerated aryl radical under oxidative destannylation of the aryl stannane, and the electron-activated aryl iodide, resulting into the aromatic C-C bond formation reaction. The visible light-promoted Stille-type coupling reaction using the polymer-based pure organic photocatalyst offers a simple, sustainable, and more economic synthetic pathway toward palladium-free aromatic C-C bond formation.

| S-EPMC5566346 | biostudies-literature

From pH- to Light-Response: Postpolymerization Modification of Polymer Brushes Grafted onto Microporous Polymeric Membranes.

Project description:A microporous pH- and light-responsive membrane that enables remote control over its interfacial properties has been fabricated. pH-Responsiveness was imparted to a porous polypropylene film via grafting of poly(methacrylic acid) brushes from the substrate using argon-plasma-induced free-radical graft polymerization. Morphological changes as a function of grafting level were analyzed using atomic force microscopy. Conversion into a light-responsive membrane was performed via postpolymerization modification to covalently attach photochromic spiropyran moieties to the grafted polymer brushes. Reversible switches in wettability and permeability were determined upon changing from acidic to basic pH or upon alternating UV- and visible-light irradiation. Additionally, light-responsive membranes show a switch in color upon UV exposure.

| S-EPMC6641005 | biostudies-literature

Adsorption and visible-light photodegradation of organic dyes with TiO<sub>2</sub>/conjugated microporous polymer composites.

Project description:A series of composite materials made of TiO2 and conjugated microporous polymers (CMPs) were prepared with a hydrothermal method and used as both adsorbents and photocatalysts for the adsorption and visible-light photodegradation of organic dyes in aqueous solutions. It is found that the blending of CMPs can significantly improve both the adsorption capacity and the photocatalytic degradation activity of TiO2 towards organic dyes.

| S-EPMC9086925 | biostudies-literature

Microporous polymer adsorptive membranes with high processing capacity for molecular separation.

Project description:Trade-off between permeability and nanometer-level selectivity is an inherent shortcoming of membrane-based separation of molecules, while most highly porous materials with high adsorption capacity lack solution processability and stability for achieving adsorption-based molecule separation. We hereby report a hydrophilic amidoxime modified polymer of intrinsic microporosity (AOPIM-1) as a membrane adsorption material to selectively adsorb and separate small organic molecules from water with ultrahigh processing capacity. The membrane adsorption capacity for Rhodamine B reaches 26.114 g m-2, 10-1000 times higher than previously reported adsorptive membranes. Meanwhile, the membrane achieves >99.9% removal of various nano-sized organic molecules with water flux 2 orders of magnitude higher than typical pressure-driven membranes of similar rejections. This work confirms the feasibility of microporous polymers for membrane adsorption with high capacity, and provides the possibility of adsorptive membranes for molecular separation.

| S-EPMC9296620 | biostudies-literature

Extraordinary capability for water treatment achieved by a perfluorous conjugated microporous polymer.

Project description:Oils, organic solvents, dyes, and heavy metal ions are primary pollutants in water resources. Currently, no sorbent material can effectively remove these types of pollutants simultaneously. Here we report a perfluorous conjugated microporous polymer with superhydrophobicity and a large surface area, which exhibits outstanding adsorption capacities, kinetics, and recyclability for a wide range of organic solvents, oils, dyes, and heavy metal ions. The adsorption capacities of this polymer, 1376.7 mg g(-1) for Congo red, 808.2 mg g(-1) for Pb(II) and 303.2 mg g(-1) for As(V), are higher than the adsorption capacities of any previously described porous materials. Our theoretical calculation reveals that the superior properties of this polymer are due to fluorination and triple bonds within the polymer. A benchmark experiment indicates that this polymer can efficiently remove these pollutants simultaneously. Application of this polymer may lead to the development of next-generation reusable and portable water purification appliances.

| S-EPMC4431420 | biostudies-literature

π-Conjugated Microporous Polymer Films: Designed Synthesis, Conducting Properties, and Photoenergy Conversions.

Project description:Conjugated microporous polymers are a unique class of polymers that combine extended π-conjugation with inherent porosity. However, these polymers are synthesized through solution-phase reactions to yield insoluble and unprocessable solids, which preclude not only the evaluation of their conducting properties but also the fabrication of thin films for device implementation. Here, we report a strategy for the synthesis of thin films of π-conjugated microporous polymers by designing thiophene-based electropolymerization at the solution-electrode interface. High-quality films are prepared on a large area of various electrodes, the film thickness is controllable, and the films are used for device fabrication. These films are outstanding hole conductors and, upon incorporation of fullerenes into the pores, function as highly efficient photoactive layers for energy conversions. Our film strategy may boost the applications in photocatalysis, energy storage, and optoelectronics.

| S-EPMC4678513 | biostudies-literature

Nano-scale charge trapping memory based on two-dimensional conjugated microporous polymer.

Project description:There is a growing interest in new semiconductor nanostructures for future high-density high-performance flexible electronic devices. Two-dimensional conjugated microporous polymers (2D-CMPs) are promising candidates because of their inherent optoelectronic properties. Here, we are reporting a novel donor-acceptor type 2D-CMP based on Pyrene and Isoindigo (PI) for a potential nano-scale charge-trapping memory application. We exfoliated the PI polymer into ~ 2.5 nm thick nanoparticles (NPs) and fabricated a Metal-Insulator-Semiconductor (MIS) device with PI-NPs embedded in the insulator. Conductive AFM (cAFM) is used to examine the confinement mechanism as well as the local charge injection process, where ultrathin high-κ alumina supplied the energy barrier for confining the charge carrier transport. We have achieved a reproducible on-and-off state and a wide memory window (ΔV) of 1.5 V at a relatively small reading current. The device displays a low operation voltage (V < 1 V), with good retention (104 s), and endurance (103 cycles). Furthermore, a theoretical analysis is developed to affirm the measured charge carriers' transport and entrapment mechanisms through and within the fabricated MIS structures. The PI-NPs act as a nanoscale floating gate in the MIS-based memory with deep trapping sites for the charged carriers. Moreover, our results demonstrate that the synthesized 2D-CMP can be promising for future low-power high-density memory applications.

| S-EPMC10620224 | biostudies-literature

Selective Blocking Property of Microporous Polymer Membranes Fabricated by Chemical Vapor Deposition.

Project description:Poly-p-xylylene films have been utilized as protective and barrier layers for gases and solvents on electronic and implantable devices. Here we report a new approach to create highly permeable and selective nanofiltration membranes coated with microporous poly-p-xylylene nanofilms fabricated through a dry chemical vapor deposition process by using [2.2]paracyclophanes derivatives on ultrafiltration membranes. The introduction of crosslinking points into rigid poly-p-xylylenes enhanced microporosity and mechanical strength due to insufficient packing and depression of structural relaxation among polymer chains in three-dimensional networks. Crosslinked nanofilms with thicknesses down to 50 nm showed outstanding permeability for water and alcohols at a pressure difference of 0.5 MPa and exhibited higher rejection ratios for water-soluble organic dyes than non-crosslinked nanofilms. Poly-p-xylylene nanofilms also showed an excellent blocking property for non-polar organic solvent permeation through specific interaction of hydrophilic pores with organic solvents.

| S-EPMC5688126 | biostudies-literature

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