Facile construction of heterogeneous dual-ionic poly(ionic liquid)s for efficient and mild conversion of CO2 into cyclic carbonates.

In the context of peaking carbon dioxide emissions and carbon neutrality, development of feasible methods for converting CO2 into high value-added chemicals stands out as a hot subject. In this study, P[D+COO-][Br-][DBUH+], a series of novel heterogeneous dual-ionic poly(ionic liquid)s (PILs) were synthesized readily from 2-(dimethylamino) ethyl methacrylate (DMAEMA), bromo-substituted aliphatic acids, organic bases and divinylbenzene (DVB). The structures, compositions and morphologies were characterized or determined by nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), infrared spectroscopy (IR), scanning electron microscopes (SEM), and Brunauer-Emmett-Teller analysis (BET), etc. Application of the P[D+COO-][Br-][DBUH+] series as catalysts in converting CO2 into cyclic carbonates showed that P[D+COO-][Br-][DBUH+]-2/1/0.6 was able to catalyze epiclorohydrin-CO2 cycloaddition the most efficiently. This afforded chloropropylene carbonate (CPC) in 98.4% yield with ≥ 99% selectivity in 24 hr under solvent- and additive-free conditions at atmospheric pressure. Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance. In addition, it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields. Finally, key catalytic active sites were probed, and a reasonable mechanism was proposed accordingly. In summary, this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides a mild and environmentally benign approach to the fixation and utilization of carbon dioxide.

Simple strategy of the use of pharmaceutically functionalized ionic liquids in a new generation of polymer nanocarriers for the combined delivery of ionic p-aminosalicylate and ampicillin.

Single and dual bioactive linear poly(ionic liquid)s (PIL) were synthesized for use as nanocarriers in drug delivery systems (DDS). These PILs were obtained through the (co)polymerization of the choline-based monomeric ionic liquids (MIL) with pharmaceutical anions possessing antibacterial properties, specifically [2-(methacryloyloxy)ethyl]trimethyl-ammonium with ampicillin and p-aminosalicylate (TMAMA/AMP and TMAMA/PAS). The copolymers exhibited varying chain lengths defined by a degree of polymerization (DPn = 122-370), and differing contents of ionic fraction and drugs (TMAMA 61-92 %, AMP 61-93 % and PAS 16-21 %). These parameters were adjustable by the monomer conversion (33-92 %) and the initial ratio of comonomers. In aqueous solution, the polymer particles reached nanosizes, i.e. 190-328 nm for AMP systems and 200-235 nm for AMP/PAS systems. In the release process, the pharmaceutical anions were released through exchange by phosphate anions in PBS at pH 7.4 at 37 °C. Depending on the copolymer composition the release of AMP was attained in 72-100 % (11.1-19.5 µg/mL) within 26 h by the single drug systems, while the dual drug systems released 61-100 % of AMP (14.8-24.7 µg/mL) and 82-100 % of PAS (3.1-4.8 µg/mL) within 72 h. The effectiveness in the drug delivery of the designed TMAMA polymers seems to be promising for future applications in antibiotic therapy and the combined therapy.

Copper-Free Synthesis of Cationic Glycidyl Triazolyl Polymers.

Copper-free synthesis of cationic glycidyl triazolyl polymers (GTPs) is achieved through a thermal azide-alkyne cycloaddition reaction between glycidyl azide polymer and propiolic acid, followed by decarboxylation and quaternization of the triazole unit. For synthesizing nonfunctionalized GTP (GTP-H), a microwave-assisted method enhances the decarboxylation reaction of carboxy-functionalized GTP (GTP-COOH). Three variants of cationic GTPs with different N-substituents [N-ethyl, N-butyl, and N-tri(ethylene glycol) monomethyl ether (EG3)] are synthesized. The molecular weight of GTP-H is determined via size exclusion chromatography. Thermal properties of all GTPs are characterized using differential scanning calorimetry and thermogravimetric analysis. The ionic conductivities of these cationic GTPs are assessed by impedance measurements. The conducting ion concentration and mobility are calculated based on the electrode polarization model. Among three cationic GTPs, the GTP with the N-EG3 substituent exhibits the highest ionic conductivity, reaching 6.8 × 10-6 S cm-1 at 25 °C under dry conditions. When compared to previously reported reference polymers, the reduction of steric crowding around the triazolium unit is considered to be a key factor in enhancing ionic conductivity.

Piperazinium Poly(Ionic Liquid)s as Solid Electrolytes for Lithium Batteries.

Poly(ionic liquid)s combine the unique properties of ionic liquids (ILs) within ionic polymers holding significant promise for energy storage applications. It is reported here the synthesis and characterization of a new family of poly(ionic liquid)s synthesized from cationic piperazinium ionic liquid monomers. The cationic poly(acrylamide piperazinium) in combination with sulfonamide anions like bis(trifluoromethanesulfonyl) imide (TFSI) and bis(fluorosulfonyl) imide (FSI) are characterized as solid polymer electrolytes. The polymer electrolytes in combination with pyrrolidonium ILs and LiFSI show high ionic conductivity, 5×10-3 S cm-1 at 100 °C. Piperazinium polymer electrolytes show excellent compatibility with lithium metal reversible plating and stripping at high current density and low temperature 40 °C.

Adhesive Zwitterionic Poly(ionic liquid) with Unprecedented Organic Solvent Resistance.

The resistance of adhesives to organic solvents is of paramount importance in diverse industries. Unfortunately, many currently available adhesives exhibit either weak intermolecular chain interactions, resulting in insufficient resistance to organic solvents, or possess a permanent covalent crosslinked network, impeding recyclability. This study introduces an innovative approach to address this challenge by formulating zwitterionic poly(ionic liquid) (ZPIL) derivatives with robust dipole-dipole interactions, incorporating sulfonic anions and imidazolium cations. Due to its unique dynamic and electrostatic self-crosslinking structure, the ZPIL exhibits significant adhesion to various substrates and demonstrates excellent recyclability even after multiple adhesion tests. Significantly, ZPIL exhibits exceptional adhesion stability across diverse nonpolar and polar organic solvents, including ionic liquids, distinguishing itself from nonionic polymers and conventional poly(ionic liquid)s. Its adhesive performance remains minimally affected even after prolonged exposure to soaking conditions. The study presents a promising solution for the design of highly organic solvent-resistant materials for plastics, coatings, and adhesives.

Poly(ionic liquid)s-Based Thermal-Responsive Microgel for Use as SERS Substrates with "ON-OFF" Switchable Effect.

A temperature-responsive surface-enhanced Raman scattering (SERS) substrate with "ON-OFF" switching based on poly(ionic liquid)s (PILs) block copolymer microgels have been designed and synthesized. The PIL units act as a joint component to anchor the gold nanoparticles (AuNPs) and analytes onto poly(N-isopropylacrylamide) (PNIPAm). This anchor allows the analytes to be fixed at the formed hot spots under temperature stimulus. Owing to the regulation of the PNIPAm segment, the SERS substrates exhibit excellent thermally responsive SERS activity with a reversible "ON-OFF" effect. Additionally, because of the anion exchange of PILs, microgels can introduce new analytes, which offers more flexibility for the system. The substrate shows excellent reversibility, controllability, and flexibility of SERS activity, which is expected to have a broad application in the field of practical SERS sensors.

1,3,4,5-Tetrasubstituted Poly(1,2,3-triazolium) Obtained through Metal-Free AA+BB Polyaddition of a Diazide and an Activated Internal Dialkyne.

A tetra(ethylene glycol)-based 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) is synthesized in two steps including: i) the catalyst-free polyaddition of a diazide and an activated internal dialkyne and ii) the N-alkylation of the resulting 1,2,3-triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3-triazole)s are obtained via AA+BB polyaddition using copper(I)-catalyzed alkyne-azide cycloaddition or metal-free thermal alkyne-azide cycloaddition (TAAC). Poly(1,2,3-triazole)s with higher molar masses are obtained in higher yields by TAAC polyaddition. A 1,3,4-trisubstituted poly(1,2,3-triazolium) structural analog obtained by TAAC polyaddition using a terminal activated dialkyne and subsequent N-alkylation of the 1,2,3-triazole groups enables discussing the influence of the methyl group in the C-4 or C-5 position on thermal and ion conducting properties. Obtained polymers are characterized by 1H, 13C, and 19F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and broadband dielectric spectroscopy. The targeted 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) exhibits a glass transition temperature of -23 °C and a direct current ionic conductivity of 2.0 × 10-6 S cm-1 at 30 °C under anhydrous conditions. The developed strategy offers opportunities to further tune the electron delocalization of the 1,2,3-triazolium cation and the properties of poly(1,2,3-triazolium)s using this additional substituent as structural handle.

Studies on Composite Solid Electrolytes with a Dual Selective Confinement Interface Structure of Anions for High-Performance Lithium Metal Batteries.

Solid-state lithium batteries (SSLBs) have attracted much attention due to their good thermal stability and high energy density. However, solid-state electrolytes with low conductivity and prominent interfacial issues have hindered the further development of SSLBs. In this research, inspired from a selective confinement structure of anions, a novel HMOF-DNSE composite solid electrolyte with a dual selective confinement interface structure is proposed based on the semi-interpenetrating structure generated by poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), poly(di-n-butylmethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI), and a metal-organic frameworks MOF derivative (HMOF) as a filler. The dual-network structure of PVDF-HFP/PDADMATFSI combined with HMOF formed a dual selective confinement interface structure to confine out the movement of large anions TFSI-, thereby enhancing the transfer ability of Li+. Subsequently, the addition of HMOF further improves the transfer of Li+ by binding up TFSI- through its crystal structure. The results show that HMOF-DNSE possesses a high room-temperature ionic conductivity (0.7 mS cm-1), a wide electrochemical window (up to 4.5 V), and a high Li+ transfer number (tLi+) (0.56). LiFePO4/HMOF-DNSE/Li cell shows an excellent capacity of 141.5 mAh g-1 at 1C rate under room temperature, with a high retention of 80.1% after 500 cycles. The material design strategy, which is based on selective confinement interface structures of anions, offers valuable insights into enhancing the electrochemical performance of solid-state lithium batteries.

Ionic Liquid-Based Polymer Matrices for Single and Dual Drug Delivery: Impact of Structural Topology on Characteristics and In Vitro Delivery Efficiency.

Previously reported amphiphilic linear and graft copolymers, derived from the ionic liquid [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMAMA_Cl‾), along with their conjugates obtained through modification either before or after polymerization with p-aminosalicylate anions (TMAMA_PAS‾), were employed as matrices in drug delivery systems (DDSs). Based on the counterion type in TMAMA units, they were categorized into single drug systems, manifesting as ionic polymers with chloride counterions and loaded isoniazid (ISO), and dual drug systems, featuring ISO loaded in self-assembled PAS conjugates. The amphiphilic nature of these copolymers was substantiated through the determination of the critical micelle concentration (CMC), revealing an increase in values post-ion exchange (from 0.011-0.063 mg/mL to 0.027-0.181 mg/mL). The self-assembling properties were favorable for ISO encapsulation, with drug loading content (DLC) ranging between 15 and 85% in both single and dual systems. In vitro studies indicated ISO release percentages between 16 and 61% and PAS release percentages between 20 and 98%. Basic cytotoxicity assessments using the 2,5-diphenyl-2H-tetrazolium bromide (MTT) test affirmed the non-toxicity of the studied systems toward human non-tumorigenic lung epithelial cell line (BEAS-2B) cell lines, particularly in the case of dual systems bearing both ISO and PAS simultaneously. These results confirmed the effectiveness of polymeric carriers in drug delivery, demonstrating their potential for co-delivery in combination therapy.

Starch hydrogel with Poly(ionic liquid)s grafted SiO2 for efficient desalination and wastewater purification.

Solar-driven interface evaporation is promising to alleviate the fresh water scarcity in an economical and sustainable way. However, most of currently reported photothermal conversion materials (PMs) are time-consuming costly, inefficient, or complex preparation process, which causes low utilization efficiency, and difficult to be practical for large-scale application. To solve this problem, a facile and green strategy for preparing hydrogel evaporator (SiO2-PILs/starch) by grafting poly(ionic liquid)s onto silica and doping it with starch is proposed. Benefiting from the broad solar absorption (ca.91 %), strong hydrophilic, and superb salt tolerance and stain resistance of SiO2-PILs/starch. Under 1 sun irradiation, the SiO2-PILs/starch achieves a remarkable solar evaporation efficiency of 91.72 % in pure water and 81.45 % in 20 wt% NaCl solution, respectively. In particular, SiO2-PILs/starch exhibited outstanding long-term salt stability (8 h) and crystalline salt can be self-cleaned in the dark environment. It is worth noting that the prepared hydrogel also possesses a satisfied evaporation efficiency of 75.84 % in oily wastewater (3 wt% n-hexadecane solution) due to its excellent water retention. These properties of SiO2-PILs/starch may provide desperately needed solution for efficient desalination and guaranteed high applicability and durability in practice.

Facile Strategy to Prepare Poly(ionic liquid)-Coated Solid Polymer Electrolytes through Layer-by-Layer Assembly.

The inability of solid polymer electrolytes to preserve strong mechanical strength with high ionic conductivity hinders the commercialization of lithium metal batteries (LMBs). The success of fabricating layer-by-layer (LbL)-assembled electrolytes has realized the application of flexible solid polymer electrolytes in electrochemical devices. Here, we demonstrate a rational strategy to construct solid electrolytes coated with multiple ultrathin layers of polyanions (poly(sodium 4-styrenesulfonate)) and polycations (linear poly(1-butyl-3-(4-vinylbenzyl)-1H-imidazolium chloride) (BVIC)/linear poly(PEG4-VIC)/SiO2-g-poly(PEG4-VIC)) using an LbL assembly method. Poly(ionic liquid) backbones and PEG side groups are employed to facilitate the transport of lithium ions via the segmental motion of the macromolecular matrix. The fabricated free-standing membranes exhibited good ionic conductivities of 9.03-10 × 10-4 S cm-1. Furthermore, a Li/LiFePO4 cell assembled with the LbL-membrane electrolytes exhibits an initial high discharge capacity of 143-158 mAhg-1 at 60 °C with high columbic efficiency. This approach, which combines polymer synthesis and LbL self-assembly, is an effective and facile route to fabricate solid polymer electrolyte membranes with superior ionic conductivity and mechanical robustness, which are useful for electrochemical devices and high-voltage battery applications.

Antibacterial, anti-inflammatory and wet-adhesive poly(ionic liquid)-based oral patch for the treatment of oral ulcers with bacterial infection.

Oral aphthous ulcers are a common inflammatory efflorescence of oral mucosa, presenting as inflammation and oral mucosal damage and manifesting as pain. The moist and highly dynamic environment of the oral cavity makes the local treatment of oral aphthous ulcers challenging. Herein, a poly(ionic liquid)-based diclofenac sodium (DS)-loaded (PIL-DS) buccal tissue adhesive patch fabricated with intrinsically antimicrobial, highly wet environment adhesive properties and anti-inflammatory activities to treat oral aphthous ulcers was developed. The PIL-DS patch was prepared via polymerization of a catechol-containing ionic liquid, acrylic acid, and butyl acrylate, followed by anion exchange with DS-. The PIL-DS can adhere to wet tissues, including mucosa muscles and organs, and efficiently deliver the carried DS- at wound sites, exerting remarkable synergistic antimicrobial (bacteria and fungi) properties. Accordingly, the PIL-DS elicited dual therapeutic effects on oral aphthous ulcers with Staphylococcus aureus infection through antibacterial and anti-inflammatory activities, significantly accelerating oral aphthous ulcer healing as an oral mucosa patch. The results indicated that the PIL-DS patch, with inherently antimicrobial and wet adhesion properties, is promising for treating oral aphthous ulcers in clinical practice. STATEMENT OF SIGNIFICANCE: Oral aphthous ulcers are a common oral mucosal disease, which could lead to bacterial infection and inflammation in severe cases, especially for people with large ulcers or low immunity. However, moist oral mucosa and highly dynamic oral environment make it challenging to maintain therapeutic agents and physical barriers at the wound surface. Therefore, an innovative drug carrier with wet adhesion is urgently needed. Herein, a poly(ionic liquid)-based diclofenac sodium (DS)-loaded (PIL-DS) buccal tissue adhesive patch was developed to treat oral aphthous ulcers showing intrinsically antimicrobial and highly wet environment adhesive properties due to the presence of catechol-containing ionic liquid monomer. Additionally, the PIL-DS showed significantly therapeutic effects on oral aphthous ulcers with S. aureus infection through antibacterial and anti-inflammatory activities. We expect that our work can provide inspiration for the development of treatment for microbially infected oral ulcers.

Noble-metal-free Co-N-C catalyst derived from cellulose-based poly(ionic liquid)s for highly efficient oxygen reduction reaction.

Noble-Metal-Free nitrogen-doped carbon-based materials are promising electrocatalysts for oxygen reduction reaction (ORR), yet it remains a great challenge to construct efficient porous non-noble metal nitrogen-doped carbon (M-N-C) catalysts with uniform distribution, due to the easy aggregation of metals. Herein, we reported the synthesis and assessment of a novel and efficient noble-metal-free catalyst for oxygen reduction reaction (ORR) from pyrolysis of a cobalt-containing cellulosic poly(ionic liquid) (Co-N-C). The prepared Co-N-C catalyst possesses high surface area, hierarchical porous structure, well-dispersed Co nanoparticles and large amounts of low-coordinated Co active sites. Especially, the Co-N-C-850 sample exhibits a high ORR activity (Eonset = 0.827 V, E1/2 = 0.74 V) that can rival 20 wt% commercial Pt/C (Eonset = 0.833 V, E1/2 = 0.71 V) in alkaline media. Moreover, the Co-N-C-850 sample also shows excellent anti-methanol poisoning activity and long-term stability toward ORR compared with commercial Pt/C. Our study provides a promising avenue both for the development of non-noble M-N-C catalysts for fuel cells and the functional utilization of cellulose.

Synthesis and Characterization of Linear Copolymers Based on Pharmaceutically Functionalized Monomeric Choline Ionic Liquid for Delivery of p-Aminosalicylate.

Bioactive linear poly(ionic liquid)s (PIL) were designed as carriers in drug delivery systems (DDS). Their synthesis was based on a monomeric ionic liquid (MIL) with a relevant pharmaceutical anion to create therapeutically functionalized monomers, which further can be used in the controlled atom transfer radical polymerization (ATRP). The presence of chloride counterions in the quaternary ammonium groups of choline MIL, e.g., [2-(methacryloyloxy)ethyl]trimethyl-ammonium chloride (ChMACl), was stimulated to undergo the anion exchange with p-aminosalicylate sodium salt (NaPAS) as the source of the pharmaceutical anion with antibacterial activity. The resultant [2-(methacryloyloxy)ethyl]trimethylammonium p-aminosalicylate (ChMAPAS) was copolymerized to attain the well-defined linear choline-based copolymers with various contents of PAS anions (24-42%), which were regulated by the initial ratio of ChMAPAS to MMA and conversion degree. The length of polymeric chains was evaluated by the total monomer conversion (31-66%) yielding degree of polymerization (DPn = 133-272). Depending on the polymer carrier composition, PAS anions were exchanged by 60-100% within 1 h, 80-100% within 4 h, and completely after 24 h by phosphate anions in PBS imitating a physiological fluid.

Poly(ionic liquid)s for Photo-Driven CO2 Cycloaddition: Electron Donor-Acceptor Segments Matter.

CO2 cycloaddition with epoxides is a key catalytic procedure for CO2 utilization. Several metal-based catalysts with cocatalysts are developed for photo-driven CO2 cycloaddition, while facing difficulties in product purification and continuous reaction. Here, poly(ionic liquid)s are proposed as metal-free catalysts for photo-driven CO2 cycloaddition without cocatalysts. A series of poly(ionic liquid)s with donor-acceptor segments are fabricated and their photo-driven catalytic performance (conversion rate of 83.5% for glycidyl phenyl ether) outstrips (≈4.9 times) their thermal-driven catalytic performance (17.2%) at the same temperature. Mechanism studies confirm that photo-induced charge separation is promoted by the donor-acceptor segments and can accelerate the CO2 cycloaddition reaction. This work paves the way for the further use of poly(ionic liquid)s as catalysts in photo-driven CO2 cycloaddition.

Conjugated Poly(ionic liquid)-Based Nanoporous Membrane for Rapid Moisture Response.

Stimuli-responsive nanoporous materials represent a newly emerging category of functional materials, for which instant and significant response behavior is strongly demanded but still challenging. Herein, a new kind of conjugated poly(ionic liquid)s (PILs) synthesized via a simple one-pot spontaneous nucleophilic substitution and polymerization between 4,4'-vinylenedipyridine and propargyl bromide is reported. A nanoporous membrane actuator is further developed via ionic complexation between the current PIL and trimesic acid. The actuator carries a gradient density in the hydrophobicity content along the membrane cross-section, which results in a fast response to moisture.

Rapidly Photocurable Solid-State Poly(ionic liquid) Ionogels For Thermally Robust and Flexible Electrochromic Devices.

Formation of ionogels through in situ polymerization can effectively improve electrolyte processability; however, the curing process has been slow and oxygen-sensitive. Considering the low oxygen solubility of poly(ionic liquid)s (PILs), in situ polymerized ionogels are designed to realize excellent electrolytes. Herein, two in situ polymerized ionogels (PIL A & PIL B) are formulated, and they can be rapidly photocured within a minute. The ionogels are highly transparent, stretchable, and exhibit excellent physicochemical stability, including thermal, electrochemical, and air stability, allowing them to perform in various conditions. Benefitting from these properties, two high-performance electrochromic devices (ECDs) are assembled, with iron-centered coordination polymer (FeCP) and tungsten oxide (P-WO3 ) electrochromic materials, achieving high color contrast (45.2% and 56.4%), fast response time (1.5/1.9 and 1.7/6.4 s), and excellent cycling endurance (>90% retention over 3000 cycles). Attributed to the thermal robustness of the ionogels, the ECDs can also be operated over a wide temperature range (-20 to 100 °C). With the use of deformable substrates (e.g., ultrathin ITO glass), curved electrochromic eye protector and flexible electrochromic displays are realized, highlighting their potential use in futuristic wearables.

Poly(ionic liquid) Nanovesicle-Templated Carbon Nanocapsules Functionalized with Uniform Iron Nitride Nanoparticles as Catalytic Sulfur Host for Li-S Batteries.

Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazolium-based PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C"). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g-1 at 0.5 C initially, and a remaining value of 930 mAh g-1 after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g-1 at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion.

A Computer Simulation Study of Thermal and Mechanical Properties of Poly(Ionic Liquid)s.

Thermal and mechanical properties of poly(ionic liquid)s (PILs), an epoxidized ionic liquid-amine network, are studied via molecular dynamics simulations. The poly(ionic liquid)s are designed with two different ionic liquid monomers, 3-[2-(Oxiran-2-yl)ethyl]-1-{4-[(2-oxiran-2-yl)ethoxy]phenyl}imidazolium (EIM2) and 1-{4-[2-(Oxiran-2-yl)ethyl]phenyl}-3-{4-[2-(oxiran-2-yl)ethoxy]benzyl}imidazolium (EIM1), each of which is networked with tris(2-aminoethyl)amine, paired with different anions, bis(trifluoromethanesulfonyl)imide (TFSI-) and chloride (Cl-). We investigate how ionic liquid monomers with high ionic strength affect structures of the cross-linked polymer networks and their thermomechanical properties such as glass transition temperature (Tg) and elastic moduli, varying the degree of cross-linking. Strong electrostatic interactions between the cationic polymer backbone and anions build up their strong structures of which the strength depends on their molecular structures and anion size. As the anion size decreases from TFSI- to Cl-, both Tg and elastic moduli of the PIL increase due to stronger electrostatic interactions present between their ionic moieties, making it favorable for the PIL to organize with stronger bindings. Compared to the EIM2 monomer, the EIM1 monomers and TFSI- ions generate a PIL with higher Tg and elastic moduli. This attributes to the less flexible structure of the EIM1 monomer for the chain rotation, in which steric hindrance by ring moieties in the EIM1-based PIL enhances their structural rigidity. The π-π stacking structures between the rings are found to increase in EIM1-based PIL compared to the EIM2-based one, which becomes stronger with smaller Cl- ion rather than TFSI-. The effect of the degree of the cross-linking on thermal and mechanical properties is also examined. As the degree of cross-linking decreases from 100% to 60%, Tg also decreases by a factor of 10-20%, where the difference among the given PILs becomes decreased with a lower degree of cross-linking. Both the Young's (E) and shear (G) moduli of all the PILs decrease with degree of cross-linking, which the reduction is more significant for the PIL generated with EIM2 monomers. Transport properties of anions in PILs are also studied. Anions are almost immobilized globally with very small structural fluctuations, in which Cl- presents lower diffusivity by a factor of ~2 compared to TFSI- due to their stronger binding to the cationic polymer backbone.

One-pot fabrication of poly (ionic liquid)s functionalized magnetic adsorbent for efficient enrichment of phenylurea herbicides in environmental waters.

Efficient capture is an essential procedure in the highly sensitive monitoring of phenylurea herbicides (PUHs) in various environmental waters. Herein, a new poly (ionic liquid)s functionalized magnetic adsorbent (PFMA) was conveniently fabricated by means of "one-pot" strategy. The preparation procedure was quite simple by mixing 1-allyl-3-methylimidazoliumbis[(trifluoromethy)sulfonyl]imide, ethylene glycol dimethacrylate, Fe3+, Fe2+, mixed solution of dimethyl sulfoxide/H2O and azobisisobutyronitrile in one pot, and the total reaction time was just 3.0 h which was far shorter than that needed in previous approaches. A series of characterized techniques were employed to observe and inspect the morphology, structure and magnetic properties of prepared PFMA. Results revealed that the adsorbent contained abundant functional groups and superior magnetic property. Combing with magnetic solid-phase extraction (MSPE) format, the resultant PFMA displayed high capture capability towards studied PUHs through multiple interactions, and the enrichment factors were in the range of 126-227. Under the selected extraction parameters, the introduced PFMA/MSPE was combined with HPLC equipped with diode array detector (HPLC/DAD) to measure investigated PUHs at trace levels in various environmental waters. Wide linear range (0.010-200 µg/L), low limit of detection (0.0025-0.015 µg/L) and good precision (RSDs<10%) were achieved. The reliability and practicality of established approach was demonstrated by quantifying trace studied PUHs in various waters. Satisfactory fortified recoveries (80.2-119%) and repeatability were achieved. The results well evidence that the prepared PFMA is a good alternative for capture PUHs, and the introduced approach has wide prospect in the analyzing trace levels of PUHs in water and other complex samples.