Precise Construction of Nitrogen-Enriched Porous Ionic Polymers as Highly Efficient Sulfur Dioxide Adsorbent.

Porous ionic polymers with unique features have exhibited high performance in various applications. However, the fabrication of functional porous ionic polymers with custom functionality and porosity for efficient removal of low-concentration SO2 remains challenging. Herein, a novel nitrogen-enriched porous ionic polymer NH2Py-PIP is prepared featuring high-content nitrogen sites (15.9 wt.%), adequate ionic sites (1.22 mmol g-1), and a hierarchical porous structure. The proposed construction pathway relies on a tailored nitrogen-functionalized cross-linker NH2Py, which effectively introduces abundant functional sites and improves the porosity of porous ionic polymers. NH2Py-PIP with a well-engineered SO2-affinity environment achieves excellent SO2/CO2 selectivity (1165) and high SO2 adsorption capacity (1.13 mmol g-1 at 0.002 bar), as well as enables highly efficient and reversible dynamic separation performance. Modeling studies further elucidate that the nitrogen sites and bromide anions collaboratively promote preferential adsorption of SO2. The unique design in this work provides new insights into constructing functional porous ionic polymers for high-efficiency separations.

Preparation of biochars by conventional pyrolysis of herbal waste and their potential application for adsorption and energy purposes.

The nettle, sage, mint and lemon balm herbs were used for biochars preparation. The physicochemical parameters of obtained materials were related to the lignocellulose composition of the precursors. It has been proved that the content of mineral substance has a significant influence on development of surface area, whereas the amount of hemicellulose affects the content of surface functional groups. It has been also shown that the obtained biochars are characterized by great energy parameters. The higher heating values (HHV) of the carbonaceous materials are comparable to the typical energy sources. The greatest HHV value (20.36 MJ/kg) was characteristic for the biochar obtained by pyrolysis of the lemon balm. In addition, the biochars were used for ionic polymers adsorption from one- and two-components solutions. Despite the adsorbed amounts of macromolecules are not great is has been proved that polyethylenimine and polyacrylic acid have positive influence on their mutual adsorption.

Palladium and Ruthenium Dual-Single-Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption.

Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1 -Ru1 single-atom-sites supported on porous ionic polymers (Pd1 -Ru1 /PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd- or Ru-site catalyst, the dual single-atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single-Ru site exhibited a strong CO adsorption energy of -1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1 -Ru1 /PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1 /PIPs for the rate-determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single-site catalysts at the molecular level.

Facile Construction of Carboxyl-Functionalized Ionic Polymer towards Synergistic Catalytic Cycloaddition of Carbon Dioxide into Cyclic Carbonates.

The development of bifunctional ionic polymers as heterogeneous catalysts for effective, cocatalyst- and metal-free cycloaddition of carbon dioxide into cyclic carbonates has attracted increasing attention. However, facile fabrication of such polymers having high numbers of ionic active sites, suitable types of hydrogen bond donors (HBDs), and controlled spatial positions of dual active sites remains a challenging task. Herein, imidazolium-based ionic polymers with hydroxyl/carboxyl groups and high ionic density were facilely prepared by a one-pot quaternization reaction. Catalytic evaluation demonstrated that the presence of HBDs (hydroxyl or carboxyl) could enhance the catalytic activities of ionic polymers significantly toward the CO2 cycloaddition reaction. Among the prepared catalysts, carboxyl-functionalized ionic polymer (PIMBr-COOH) displayed the highest catalytic activity (94% yield) in the benchmark cycloaddition reaction of CO2 and epichlorohydrin, which was higher than hydroxyl-functionalized ionic polymer (PIMBr-OH, 76% yield), and far exceeded ionic polymer without HBDs groups (PIMBr, 54% yield). Furthermore, PIMBr-COOH demonstrated good recyclability and wide substrate tolerance. Under ambient CO2 pressure, a number of epoxides were smoothly cycloadded into cyclic carbonates. Additionally, density functional theory (DFT) calculation verified the formation of strong hydrogen bonds between epoxide and the HBDs of ionic polymers. Furthermore, a possible mechanism was proposed based on the synergistic effect between carboxyl and Br- functionalities. Thus, a facile, one-pot synthetic strategy for the construction of bifunctional ionic polymers was developed for CO2 fixation.

Salt-Rejection Solar Absorbers Based on Porous Ionic Polymers Nanowires for Desalination.

The construction of photothermal materials with ideal salt tolerance has been a major subject for efficient solar desalination. Herein, a novel photothermal material based on porous ionic polymers (PIPs) nanowires is synthesized by Sonogashira-Hagihara cross-coupling reaction using ionic salt and alkynylbenzene as building blocks. The PIPs nanowires monolith shows abundant porosity with low density, leading a superior thermal insulation. The intrinsic superhydrophilicity of PIPs nanowires endows it with desired water transportation ability. By facile spraying Chinese carbon-ink on the PIPs nanowires monolith, its light absorption can be enhanced to be 90%. Based on these merits, the PIPs nanowires based photothermal materials show high solar energy conversion efficiency (81% under 1 sun irradiation). More interestingly, its inherently ionic framework can result in an ion-ion interaction between the external ions in water and ionic groups in PIPs framework, thus leading to excellent desalination ability by combing its unique superhydrophilicity, for example, no salt accumulation is observed after 6 h duration at 1 sun irradiation. Compared with the existing salt-resistant photothermal materials, the method takes the advantage of the intrinsically ionic feature of PIPs without using any artificial process, thus may open a new way for design and fabrication of high-performance salt-rejection photothermal materials.

Synthesis, Characterization, and Nanodisc Formation of Non-ionic Polymers*.

Although lipid nanodiscs are increasingly used in the structural studies of membrane proteins, drug delivery and other applications, the interaction between the nanodisc belt and the protein to be reconstituted is a major limitation. To overcome this limitation and to further broaden the scope of nanodiscs, a family of non-ionic amphiphilic polymers synthesized by hydrophobic functionalization of fructo-oligosaccharides/inulin is reported. We show the stability of lipid nanodiscs formed by these polymers against pH and divalent metal ions, and their magnetic-alignment properties. The reported results also demonstrate that the non-ionic polymers extract membrane proteins with unprecedented efficiency.

Enhanced Chemisorption and Catalytic Effects toward Polysulfides by Modulating Hollow Nanoarchitectures for Long-Life Lithium-Sulfur Batteries.

Hollow nanostructures with intricate interior and catalytic effects hold great promise for the construction of advanced lithium-sulfur batteries. Herein, a double-shelled hollow polyhedron with inlaid cobalt nanoparticles encapsulated by nitrogen-doped carbon (Co/NC) nanodots (Co-NC@Co9 S8 /NPC) is reported, which is acquired by using imidazolium-based ionic-polymer-encapsulated zeolitic imidazolate framework-67 as a core-shelled precursor. The Co/NC nanodots promote redox kinetics and chemical adsorbability toward polysulfides, while the interconnected double shells serve as a nanoscale electrochemical reaction chamber, which effectively suppresses the polysulfide shuttling and accelerates ion/electron transport. Benefiting from structural engineering and reaction kinetics modulation, the Co-NC@Co9 S8 /NPC-S electrode exhibits high cycling stability with a low capacity decay of 0.011% per cycle within 2000 cycles at 2 C. The electrode still shows high rate performance and cyclability over 500 cycles even in the case of high sulfur loading of 4.5 mg cm-2 and 75 wt% sulfur content. This work provides one type of new hollow nanoarchitecture for the development of advanced Li-S batteries and other energy storage systems.

Lower Activation Energy for Catalytic Reactions through Host-Guest Cooperation within Metal-Organic Frameworks.

Industrial synthesis is driven by a delicate balance of the value of the product against the cost of production. Catalysts are often employed to ensure product turnover is economically favorable by ensuring energy use is minimized. One method, which is gaining attention, involves cooperative catalytic systems. By inserting a flexible polymer into a metal-organic framework (MOF) host, the advantages of both components work synergistically to create a composite that efficiently fixes carbon dioxide to transform various epoxides into cyclic carbonates. The resulting material retains high yields under mild conditions with full reusability. By quantitatively studying the kinetic rates, the activation energy was calculated, for a physical mixture of the catalyst components to be about 50 % higher than that of the composite. Through the unification of two catalytically active components, a new opportunity opens up for the development of synergistic systems in multiple applications.

Ionic Polymer Microspheres Bearing a Co(III) -Salen Moiety as a Bifunctional Heterogeneous Catalyst for the Efficient Cycloaddition of CO2 and Epoxides.

We report a unique strategy to obtain the bifunctional heterogeneous catalyst TBB-Bpy@Salen-Co (TBB=1,2,4,5-tetrakis(bromomethyl)benzene, Bpy=4,4'-bipyridine, Salen-Co=N,N'-bis({4-dimethylamino}salicylidene)ethylenediamino cobalt(III) acetate) by combining a cross-linked ionic polymer with a Co(III) -salen Schiff base. The catalyst showed extra high activity for CO2 fixation under mild, solvent-free reaction conditions with no requirement for a co-catalyst. The synthesized catalyst possessed distinctive spherical structural features, abundant halogen Br(-) anions with good leaving group ability, and accessible Lewis acidic Co metal centers. These unique features, together with the synergistic role of the Co and Br(-) functional sites, allowed TBB-Bpy@Salen-Co to exhibit enhanced catalytic conversion of CO2 into cyclic carbonates relative to the corresponding monofunctional analogues. This catalyst can be easily recovered and recycled five times without significant leaching of Co or loss of activity. Moreover, based on our experimental results and previous work, a synergistic cycloaddition reaction mechanism was proposed.

Ionic Covalent Organic Frameworks with Spiroborate Linkage.

A novel type of ionic covalent organic framework (ICOF), which contains sp(3)  hybridized boron anionic centers and tunable countercations, was constructed by formation of spiroborate linkages. These ICOFs exhibit high BET surface areas up to 1259 m(2) g(-1) and adsorb a significant amount of H2 (up to 3.11 wt %, 77 K, 1 bar) and CH4 (up to 4.62 wt %, 273 K, 1 bar). Importantly, the materials show good thermal stabilities and excellent resistance to hydrolysis, remaining nearly intact when immersed in water or basic solution for two days. The presence of permanently immobilized ion centers in ICOFs enables the transportation of lithium ions with room-temperature lithium-ion conductivity of 3.05×10(-5)  S cm(-1) and an average Li(+) transference number value of 0.80±0.02. Our approach thus provides a convenient route to highly stable COFs with ionic linkages, which can potentially serve as absorbents for alternative energy sources such as H2, CH4, and also as solid lithium electrolytes/separators for the next-generation lithium batteries.

ß-Cyclodextrin-derived diallylamine salt: Synthesis and its copolymerizations.

A diallyl amine salt monomer bearing a ß-CD substituent was cyclopolymerized for the first time. The reaction of 6-O-toluenesulfonyl-ß-cyclodextrin [(C6H10O5)6-(C5H7)]-CH2OTs with diallylamine followed by protonation afforded the diallylamine salt monomer [(C6H10O5)6-(C5H7)]-CH2NH+(CH2CH=CH2)2 Cl-] (I). The cyclopolymerization of monomer I and its copolymerization with monomer [Me2N+(CH2CH=CH2)2 Cl-] (II), [-O2CCH2NH+(CH2CH=CH2)2] (III), [H2O3PCH2NH+(CH2CH=CH2)2 Cl-] (IV) or [HO2CCH2CH(CO2H)NH+(CH2CH=CH2)2 Cl-] (V) yielded a series of copolymers having residues of ß-CD and glycine or methyl phosphonate or aspartic acid. Terpolymerization in the presence of SO2 afforded polymers with alternating placements of the SO2 units. The solution properties of the pH-responsive polyzwitterions, including their viscosity, were examined. The water-insoluble terpolymer I/V/SO2 with 20 mol% ß-CD residues removed the organic micropollutant 2-naphthol from an aqueous system via host/guest complexation. This work paves the way for the possible synthesis of cross-linked polymers that can simultaneously remove organic micropollutants and toxic metal ions (by complexation with the chelating glycine, aspartic acid, and aminomethyl phosphonate ligands) from contaminated aqueous systems.

High-Surface-Area Metalloporphyrin-Based Porous Ionic Polymers by the Direct Condensation Strategy for Enhanced CO2 Capture and Catalytic Conversion into Cyclic Carbonates.

Metalloporphyrin-based porous organic polymers (POPs) that behave as advanced biomimetic nanoreactors have drawn continuous attention for heterogeneous CO2 catalysis in the past decades. Inspired by the double activation model of epoxides, the design and synthesis of metalloporphyrin-based porous ionic polymers (PIPs) are considered as one of the most promising approaches for converting CO2 to cyclic carbonates under cocatalyst- and solvent-free conditions. To overcome the obstacle of poor reaction activity of ionic monomers or highly irregular stacking architecture, in this paper, we have proposed and demonstrated a modular bottom-up approach for constructing a series of high-surface-area metalloporphyrin-based PIPs in high yields by the direct condensation strategy, thus boosting the close contact of multiple active sites and achieving the enhanced CO2 capture and catalytic conversion into cyclic carbonates with high turnover frequencies under mild conditions. These recyclable aluminum-porphyrin-based PIPs are featured with high surface areas, prominent CO2 adsorptive capacities, rigid porphyrin skeletons, and flexible ionic pendants, as well as the matched amounts and spatial positions of metal centers and ionic sites, in which is demonstrated to be one of the quite competitive catalysts. Therefore, this strategy of introducing ionic components into the porphyrin frameworks as flexible side chains rather than main chains and adjusting the reactivity ratios of comonomers by structure-oriented methods, provides feasible guidance for the multifunctionalization of metalloporphyrin-based POPs, thereby increasing the accessibility of multiple active sites and improving their synergistic catalytic behavior.

Functional Porous Ionic Polymers as Efficient Heterogeneous Catalysts for the Chemical Fixation of CO2 under Mild Conditions.

The development of efficient and metal-free heterogeneous catalysts for the chemical fixation of CO2 into value-added products is still a challenge. Herein, we reported two kinds of polar group (-COOH, -OH)-functionalized porous ionic polymers (PIPs) that were constructed from the corresponding phosphonium salt monomers (v-PBC and v-PBH) using a solvothermal radical polymerization method. The resulting PIPs (POP-PBC and POP-PBH) can be used as efficient bifunctional heterogeneous catalysts in the cycloaddition reaction of CO2 with epoxides under relatively low temperature, ambient pressure, and metal-free conditions without any additives. It was found that the catalytic activities of the POP-PBC and POP-PBH were comparable with the homogeneous catalysts of Me-PBC and PBH and were higher than that of the POP-PPh3-COOH that was synthesized through a post-modification method, indicating the importance of the high concentration catalytic active sites in the heterogeneous catalysts. Reaction under low CO2 concentration conditions showed that the activity of the POP-PBC (with a conversion of 53.8% and a selectivity of 99.0%) was higher than that of the POP-PBH (with a conversion of 32.3% and a selectivity of 99.0%), verifying the promoting effect of the polar group (-COOH group) in the porous framework. The POP-PBC can also be recycled at least five times without a significant loss of catalytic activity, indicating the high stability and robustness of the PIPs-based heterogeneous catalysts.

Detergent-Free Isolation of Membrane Proteins and Strategies to Study Them in a Near-Native Membrane Environment.

Atomic-resolution structural studies of membrane-associated proteins and peptides in a membrane environment are important to fully understand their biological function and the roles played by them in the pathology of many diseases. However, the complexity of the cell membrane has severely limited the application of commonly used biophysical and biochemical techniques. Recent advancements in NMR spectroscopy and cryoEM approaches and the development of novel membrane mimetics have overcome some of the major challenges in this area. For example, the development of a variety of lipid-nanodiscs has enabled stable reconstitution and structural and functional studies of membrane proteins. In particular, the ability of synthetic amphipathic polymers to isolate membrane proteins directly from the cell membrane, along with the associated membrane components such as lipids, without the use of a detergent, has opened new avenues to study the structure and function of membrane proteins using a variety of biophysical and biological approaches. This review article is focused on covering the various polymers and approaches developed and their applications for the functional reconstitution and structural investigation of membrane proteins. The unique advantages and limitations of the use of synthetic polymers are also discussed.

The Electrostatic Attraction and Catalytic Effect Enabled by Ionic-Covalent Organic Nanosheets on MXene for Separator Modification of Lithium-Sulfur Batteries.

It is of great significance to mediate the redox kinetics and shuttle effect of polysulfides in pursuit of high-energy-density and long-life lithium-sulfur (Li-S) batteries. Herein, a new strategy is proposed based on the electrostatic attraction and catalytic effect of polysulfides for the modification of the polypropylene (PP) separator. Guanidinium-based ionic-covalent organic nanosheets (iCON) on the surface of Ti3 C2 is presented as a coating layer for the PP separator. The synergetic effects of Ti3 C2 and iCON provide new platforms to suppress the shuttle effect of polysulfides, expedite the redox kinetics of sulfur species, and promote efficient conversion of the intercepted polysulfides. The functional separator endows carbon nanotube/sulfur cathodes with excellent electrochemical performance. The average capacity decay per cycle within 2000 cycles at 2 C is as low as 0.006%. The separator is even effective in the case of sulfur content of 90 wt% and sulfur loading of 7.6 mg cm-2 ; the reversible capacity, areal capacity, and volumetric capacity at 0.1 C are as high as 1186 mA h g-1 , 9.01 mA h cm-2 , and 1201 mA h cm-3 , respectively. This work provides a promising approach toward separator modification for the development of high-performance Li-S batteries.

Boosted activity by engineering the enzyme microenvironment in cascade reaction: A molecular understanding.

Engineering of enzyme microenvironment can surprisingly boost the apparent activity. However, the underlying regulation mechanism is not well-studied at a molecular level so far. Here, we present a modulation of two model enzymes of cytochrome c (Cty C) and d-amino acid oxidase (DAAO) with opposite pH-activity profiles using ionic polymers. The operational pH of poly (acrylic acid) modified Cyt C and polyallylamine modified DAAO was extended to 3-7 and 2-10 where the enzyme activity was larger than that at their optimum pH of 4.5 and 8.5 by 106% and 28%, respectively. The cascade reaction catalyzed by two modified enzymes reveals a 1.37-fold enhancement in catalytic efficiency compared with their native counterparts. The enzyme activity boosting is understood by performing the UV-vis/CD spectroscopy and molecular dynamics simulations in the atomistic level. The increased activity is ascribed to the favorable microenvironment in support of preserving enzyme native structures nearby cofactor under external perturbations.

Water-Soluble and Low-Toxic Ionic Polymer Dots as Invisible Security Ink for MultiStage Information Encryption.

Nanodots are attractive stimuli-responsive luminescence materials for anti-counterfeiting and information encryption. However, their applications are limited by low water solubility and single-mode information identification by naked eyes under UV light illumination. Herein, we report one type of new nanodots, main-chain imidazolium-based ionic polymer dots (IPDs). There is no edge effect in IPDs, and the ionic groups are homogenously distributed in the entire dot. IPDs exhibit high water solubility, good stability, narrow size distribution, low toxicity, and exceptional optical performance without additional modification. Written information using aqueous IPD solution is invisible in natural light, but can be recognized by a portable UV lamp. Moreover, they can be further encrypted and decrypted using easily available and nontoxic sodium carbonate and acetic acid, respectively. The encrypted information is invisible in natural light and/or UV light. This study provides a new prospect for high-level data recording and security protection by using water-soluble IPDs as invisible security ink.

Preparation of an Interpenetrating Network of a Poly(ampholyte) and a Cholesteric Polymer and Investigation of Its Hydrochromic Properties.

A new water-responsive photonic coating based on a hygroscopic amphoteric poly(ampholyte) has been developed. The material consists of an interpenetrating network between the poly(ampholyte) and a cholesteric liquid crystalline polymer that reflects light. Swelling of this hybrid material upon contact with water causes a red-shift of the reflection band. As both cation and anion are incorporated in the ionic network, this coating possesses a high stability of its water responsiveness after prolonged and/or repeated exposure to water, even if the water contains dissolved ions. In addition, optimization of the water response of the coatings is demonstrated by changing the composition of the base cholesteric mixture, and color patterns were prepared through selective UV exposure.

Dual-Ionically Bound Single-Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts.

Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh1 /PIP catalyst, featuring a new active site [Rh(CO)I3 ]2- dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO)2 I2 ]- in previous studies. Such a unique metal configuration of Rh1 /PIP leads to excellent performance in vapor-phase methanol carbonylation, outperforming commercial homo- and heterogeneous catalysts.

Synthesis of Cross-linked Ionic Poly(styrenes) and their Application as Catalysts for the Synthesis of Carbonates from CO2 and Epoxides.

A series of dicationic styrene-functionalized imidazolium-based salts, in which the two imidazolium rings are bridged by a functionalized spacer, are prepared. The salts are polymerized to afford cross-linked imidazolium-based ionic polystyrene materials, which, owing to the presence of the functionalized spaces, should be highly active organocatalysts for the cycloaddition of CO2 to epoxides to afford cyclic carbonates (CCE reaction). The catalytic activities of the polymers are evaluated in the CCE reaction. The most active catalyst incorporates a diol functionality and is active at 80 °C and a pressure of 4 bar at a loading of 5 mol %, which is comparable to the most active organocatalysts. Moreover, high yields can be obtained under atmospheric pressure upon increasing the temperature to 120 °C. Under harsher conditions, the catalyst is highly active at a loading one order of magnitude lower, highlighting the importance of benchmark conditions for the CCE reaction. Moreover, the polymer catalysts are advantageous because they can be used at low catalyst loadings, the carbonate product is easily isolated in pure form, and loss of activity of the recovered polymer catalyst is not observed during reuse.