Bifunctional Monomer Research Articles

Chemoselective Ring-Opening Polymerization of α-Methylene-δ-valerolactone Catalyzed by a Simple Organoaluminum Complex to Prepare Closed-Loop Recyclable Functional Polyester.

α-Methylene-δ-valerolactone (MVL) as a bio-renewable bifunctional monomer has shown great promise to prepare closed-loop recyclable polyester with pendent functionalizable double bond. However, the chemoselective ring-opening polymerization (ROP) of MVL still faces challenges including low polymerization temperature, expensive catalyst as well as high catalyst loading. In this contribution, we present the chemoselective and controlled ROP of MVL using a simple organoaluminum complex [MeAl(BHT)2] (BHT=2,6-di-tert-butyl-4-methylphenoxy), which can be easily prepared from commercially available trimethylaluminum and 2,6-di-tert-butyl-4-methylphenol without purification. MeAl(BHT)2 exhibits much higher catalytic activity (TOF=668 h-1) than that of MeAl[Salen] (TOF=89 h-1), a commonly used organoaluminum catalyst. The high chemoselectivity and activity of MeAl(BHT)2 is proposed to originate from the cooperative activation of propagating chain-ends and monomers via the "coordination-insertion" mechanism. Remarkably, high-molecular-weight P(MVL)ROP can be prepared in bulk using MeAl(BHT)2, which is not accessible by the previous catalysts. This study may advance the development of closed-loop recyclable polymers considering the easy preparation, low cost and good catalytic performance of MeAl(BHT)2.

Recording Reflection Volume Holographic Gratings with Enhanced Performance by Two‐Stage Photopolymers Containing Bifunctional Monomers

AbstractA holographic optical waveguide (HOW) is an optimal solution for augmented reality (AR) displays, in which reflection volume holographic gratings are core optical elements. In this study, five high‐refractive‐index (≈1.6) bifunctional acrylate monomers (TPBSAs) are designed and synthesized. A series of two‐stage photopolymers are prepared using TPBSAs as writing monomers. Among them, one containing 9 wt.% TPBSA‐3 shows the best holographic recording performance with a sensitivity as high as 26.59 cm mJ−1. Using it as the recording medium, a reflection VHG can be obtained with high spatial frequency (5634 lines per mm), diffraction efficiency (97.14%), refractive index modulation (0.029), and good transparency within 400−800 nm after photobleaching. Furthermore, a HOW capable of achieving virtual and real image fusion is fabricated.

Preparation of a V–COF@SWCNTs-COOH/SPCE supported molecularly imprinted electrochemical sensor for real-time detection of trace sulfadimidine

To overcome the limitations of insufficient sensitivity and poor specificity of portable screen-printed carbon electrode-electrochemical sensors (SPCE-EC) in practical applications, we prepared carrier composites of carboxylic single-walled carbon nanotubes vertically grafted by covalent organic frameworks (v-COF@SWCNTs-COOH) and coated with a molecularly imprinted polymer (MIP) of sulfadimidine (SM2). 55 °C hot steam elution is more eco-friendly than traditional organic solvent elution. The results showed that when the mass ratio of DBA to DBA-SWCNTs was 1:1, the v-COF@SWCNTs-COOH obtained by the two-step synthesis method could increase the electrical signal up to 2.33-fold of the bare electrode. The bifunctional monomer MIP prepared on the above structure enhanced the signal response by 2.91-fold, with a high imprint factor of 20. The assembled MIP/v-COF@SWCNTs-COOH/SPCE were analyzed by differential pulse voltammetry (DPV) with a high sensitivity of 0.21 nM for LOD and 0.70 nM for LOQ. In milk and fish samples, the recovery rate was 95.0 %–104.8 %. The validation of authentic pork samples with the statutory LC-MS/MS method showed no significant difference (P > 0.05). The sensor's performance indicators remained robust after five repeated uses. Therefore, the MIP/v-COF@SWCNTs-COOH/SPCE combines the cheapness and portability of SPCE, while the sensitivity and specificity of small molecule detection were significantly improved.

Determinationof indole-3-acetic acid using disposable molecularly imprinted electrochemical sensors based on bifunctional monomers.

Stainless steel sheets were coated with carbon ink to obtain disposable carbon electrodes, which were used as supports for moleculary imprinted polymer (MIP) electrochemical sensors by electropolymerizing o-phenylenediamine and o-aminophenol along with indole-3-acetic acid (IAA) as the template. After optimization, the MIP biosensors could be used for sensitive and selective detection of IAA with the limit of quantification of 0.1µM. Our experimental results showed that stable and reproducible electrochemical responses could be achieved for the disposable MIP biosensors. This approach wassuccessfully used for detection of IAA in different tissues of pea sprouts. This study reveals the potential of MIP electrochemical sensors in practical applications and shrinks the trench between the research and the real world.

Toward Molecular Textiles: Synthesis and Characterization of Molecular Patches.

This works describes a new step into the assembly of molecular textiles by the use of covalent templating. To establish a well-founded base and to tackle pre-mature obstacles, expected during the fabrication of the desired 2D-material, we opted to investigate the in-solution synthesis of molecular patches e.g. cut-outs of a textile. A bi-functional cross-shaped monomer was designed, synthesized and was in-detail characterized by means of 1H-NMR and chiro-optical spectroscopy. In addition, x-ray structure crystallography was used to assess the absolute configuration. The monomer was used in an in-solution oligomerization to assemble the molecular patches via imine condensation, which revealed the formation of predominately dimeric patches. The imine-oligomer mixtures were further analyzed by reduction and cleaved to investigate the conditions required post mono-layer assembly. All reaction stages were followed by FT-IR and 1H-NMR analysis. Finally, we address the adsorption of the cross-shaped monomer onto a Au(111) surface, via high vacuum electrospray deposition. The subsequent annealing of the interface induced the on-surface imine condensation reaction, leading to unidimensional oligomers co-adsorbed with clusters of cyclic-dimers. Nc-AFM analysis revealed the tridimensional molecular structures, and together with electrospray deposition technique showed to be a promising pathway to investigate potential monomer candidates.

Surface amphiphilic hybrid porous polymers based on cage-like organosiloxanes for pipette tip solid-phase extraction of microcystins in water

The occurrence of microcystins (MCs) during harmful algal blooms (HABs) represents a major threat to freshwater environments. In this work, a novel surface amphiphilic hybrid porous polymers based on cage-like organosiloxanes (PCSs) was prepared for the enrichment of MCs. The copolymerization of bifunctional amphiphilic monomers, 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-benzylquininium chloride (BQN), with the cross-linker methacryl substituted polyhedral oligomeric silsesquioxane (POSS) was achieved in an ionic liquid-based porogenic medium. The hierarchical porous structure, a variety of surface functional groups and weak hydrophilicity were well characterized on the prepared materials using scanning electron microscopy, nitrogen adsorption/desorption analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, zeta potential analysis and water contact angle testing, respectively. The as-prepared surface amphiphilic PCSs was used as an adsorbent for pipette tip solid-phase extraction (PT-SPE) to enrich microcystins (MCs) from surface waters before their analysis by capillary electrochromatography (CEC) and liquid chromatography-mass spectrometry (LC-MS). Under the optimal conditions, the established PT-SPE-LC-MS method exhibited a wide linear range (10–10,000 ng L−1), low limits of detection (4.0–8.0 ng L−1) and satisfactory recoveries (89.5–102.8 %) for MCs. An adsorption mechanism involving electrostatic interactions, hydrogen bonding, hydrophilic interactions, and π-π stacking has been proposed. The findings suggest that the use of surface amphiphilic PCSs materials as adsorbents in the PT-SPE platform facilitates efficient enrichment of MCs for subsequent chromatographic analysis. These investigations offer a new perspective on the simple and uncomplicated pretreatment of complex environmental samples.

Cross-Linked Metathesis Polynorbornenes Based on Nadimides Bearing Hydrocarbon Substituents: Synthesis and Physicochemical Properties.

Metathesis homo- and copolymerization of bifunctional monomers bearing two norbornene moieties was studied. The monomers were synthesized from cis-5-norbornene-exo-2,3-dicarboxylic anhydride and various diamines (hexamethylenediamine, decamethylenediamine, 1R,3S-isophoronediamine). The metathesis homopolymerization of these bis(nadimides) in the presence of the second-generation Grubbs catalyst afforded glassy cross-linked polymers in more than 90% yields. The metathesis copolymerization of the bis(nadimides) and a monofunctional norbornene derivative containing the β-pinene fragment also resulted in insoluble cross-linked polymers in nearly quantitative yields. The structures and purity of the synthesized polymers were confirmed via IR spectroscopy and CP/MAS NMR spectroscopy. Conditions for the fabrication of mechanically strong solution-cast thin films based on copolymers synthesized from the comonomers mentioned above were determined by varying the content of the cross-linking agent. It was shown that the films made in this way are stable in a range of organic solvents and could be useful as semipermeable or membrane materials for use in liquid organic media. The permeability of the polymer films in question to 1-phenylethanol and mandelic acid was studied. The results obtained are discussed along with the data from the DSC, TGA, and powder X-ray diffraction studies of the properties of the synthesized metathesis homo- and copolymers.

Molecular imprinting electrochemical sensor based on hollow spherical PProDOT-2CH2OH and chitosan-derived carbon materials for highly sensitive detection of chloramphenicol

The misuse of chloramphenicol (CAP) has jeopardized environmental safety. It is critical to create an effective and sensitive CAP detection technique. In this paper, a composite of chitosan (CS)-derived carbon material modified hollow spherical hydroxylated poly(3,4-propylenedioxythiophene) (PProDOT-2CH2OH) was designed, which innovatively used o-phenylenediamine and p-aminobenzoic acid as bi-functional monomers to prepare molecular imprinting polymer (MIP) sensors for highly sensitive analysis and determination of CAP. It was found that the hollow spherical structure of PProDOT-2CH2OH significantly enhanced the rapid electron migration. When combined with the CS-derived carbon material, which has multi-functional sites, it improved the electrical activity and stability of the sensor. It also provided more active centers for the MIP layer to specifically recognize CAP. Therefore, this MIP sensor had a wide linear response (0.0001 ∼ 125 μM), a low limit of detection (LOD, 6.6 pM), excellent selectivity and stability. In addition, studies showed that the sensor has potential practical value. Environmental implicationChloramphenicol (CAP) is one of the most widely used antibiotics with the highest dosage due to its low price and broad-spectrum antimicrobial properties. Due to its incomplete metabolism in living organisms and its difficulty in degrading in the environment, contamination caused by it can pose a threat to public health. In this study, a novel molecularly imprinted sensor (MIP/PC2C1/GCE) was designed to provide a new idea for rapid and precise removal of CAP by adsorption. The detection of CAP in pharmaceutical, water quality, and food fields was realized.

Divalent vinyl ketones derived from fluorene: a facile synthesis of bifunctional acrylic monomers with high reactivity in thia-/aza-Michael addition and Morita-Baylis-Hillman reactions

Divalent vinyl ketones derived from fluorene: a facile synthesis of bifunctional acrylic monomers with high reactivity in thia-/aza-Michael addition and Morita-Baylis-Hillman reactions

Closed-Loop Recycling of Mixed Plastics of Polyester and CO2-Based Polycarbonate to a Single Monomer.

Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single-monomer - multiple-materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers - specifically lactone-based polyester and CO2-based polycarbonate - but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiLO) undergoes ring-opening polymerization through the lactone manifold to produce polyester, PE(BiLO), and is also applied to ring-opening copolymerization with CO2, via the epoxide manifold, to yield polycarbonate, PC(BiLO). Remarkably, a one-pot recycling process of a BiLO-derived PE/PC blend back to the constituent monomer BiLO in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

Closed‐Loop Recycling of Mixed Plastics of Polyester and CO2‐Based Polycarbonate to a Single Monomer

AbstractPhysical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO2‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiLO) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiLO), and is also applied to ring‐opening copolymerization with CO2, via the epoxide manifold, to yield polycarbonate, PC(BiLO). Remarkably, a one‐pot recycling process of a BiLO‐derived PE/PC blend back to the constituent monomer BiLO in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

A smart capecitabine imprinted nanocontainer with the dual-responsive performance to pH/NIR light

Capecitabine (CAP) is a kind of prodrug that can be metabolized into 5-fluorouracil (5-FU) in vivo, so it is usually classified as the antimetabolite fluoropyrimidine deoxynucleoside analog. In this paper, CAP, upconversion nanoparticles (UCNPs), 3,5-dicarboxy-4-methacrylate-based azobenzene (MAPDIA)/acrylic acid-functionalized gelatin, N,N′-methylene bisacrylamide (MBA), and ammonium persulfate (APS) were used as template, light trigger, bifunctional monomers, cross-linking agent and initiator, respectively. By using the free-radical polymerization and the molecular imprinting technique, the potential drug delivery nanocontainer CAP-MIP with the dual-responsive performance to pH/near infrared light (NIR) was successfully prepared. Furthermore, the characterization of CAP-MIP was also carried out by the modern instrumental analysis such as FTIR, XRD, TGA, BET and so on. The stimulus-responsive release experiment in vitro indicated the maximum cumulative release rate of CAP changed from 1.71 % to 89.54 % when the pH value in medium varied from 1.2 to 8.3, and the equilibrium release time point also greatly prolonged to 420 min from 40 min, respectively. When irradiated by 980 nm monochromatic NIR light in the same solution of pH 6.8, the maximum release rate of the sample could reach 96.21 % at 180 min, which respectively corresponded to the data of 41.84 % at 420 min under the condition of the absence of additional NIR light. In addition, CAP-MIP also had the excellent specific adsorption for CAP with the selectivity factor of 2.904 and the maximum CAP-loaded capacity of 7 mg•g−1. The above information denoted the target material should be of some potential in drug delivery system application.

Synergistic signal−amplification effect of silver nanowires and bifunctional monomers on molecularly imprinted electrochemical sensor for diuron analysis

Molecularly imprinted polymers (MIP) have been widely owing to their specificity, however, their singular structure imposes limitations on their performance. Current enhancement methods, such as doping with inorganic nanomaterials or introducing various functional monomers, are limited and single, indicating that MIP performances require further advancement. In this work, a dual−modification approach that integrates both conductive inorganic nanomaterials and diverse bifunctional monomers was proposed to develop a multifunctional MIP−based electrochemical (MMIP−EC) sensor for diuron (DU) detection. The MMIP was synthesized through a one−step electrochemical copolymerization of silver nanowires (AgNWs), o−phenylenediamine (O−PD), and 3,4−ethylenedioxythiophene (EDOT). DU molecules could conduct fluent electron transfer within the MMIP layer through the interaction between anchored AgNWs and bifunctional monomers, and the abundant recognition sites and complementary cavity shapes ensured that the imprinted cavities exhibit high specificity. The current intensity amplified by the two modification strategies of MMIP (3.7 times) was significantly higher than the sum of their individual values (3.2 times), exerting a synergistic effect. Furthermore, the adsorption performance of the MMIP was characterized by examining the kinetics and isotherms of the adsorption process. Under optimal conditions, the MMIP−EC sensor exhibits a wide linear range (0.2 ng/mL to 10 μg/mL) for DU detection, with a low detection limit of 89 pg/mL and excellent selectivity (an imprinted factor of 10.4). In summary, the present study affords innovative perspectives for the fabrication of MIP−EC sensor with superior analytical performance.

A novel ratiometric electrochemical sensing platform combined with molecularly imprinted polymer and Fe-MOF-NH2/CNTs-NH2/MXene composite for efficient detection of ofloxacin

BackgroundOfloxacin (OFL) is often abused in medicine and animal husbandry, which poses a great threat to human health and ecological environment. Therefore, it is necessary to establish efficient method to detect OFL. Electrochemical sensor has attracted widespread attention due to the advantages of low cost and fast response. However, most electrochemical sensors usually use one response signal to detect the target, which makes it sensitive to the variable background noise in the complex environment, resulting in low robustness and selectivity. The ratio detection mode and employing molecularly imprinted polymer (MIP) are two strategies to solve these problems. ResultsA novel molecular imprinting polymer-ratiometric electrochemical sensor (MIP-RECS) based on Fe-MOF-NH2/CNTs-NH2/MXene composite was prepared for the rapid and sensitive detection of OFL. The positively charged Fe-MOF-NH2 and CNTs-NH2 as interlayer spacers were introduced into the negatively charged MXene through a simple electrostatic self-assembly technique, which effectively prevented the agglomeration of MXene and increased the electrocatalytic activity. A glass carbon electrode was modified by the composite and a MIP film was electropolymerized on it using o-phenylenediamine and β-cyclodextrin as bifunctional monomers and OFL as template. Then a MIP-RECS was designed by adding dopamine (DA) into the electrolyte solution as internal reference, and OFL was quantified by the response current ratio of OFL to DA. The current ratio and the concentration of OFL displayed a satisfying linear relationship in the range of 0.1 μM–100 μM, with a limit of detection (LOD) of 13.2 nM. SignificanceCombining molecular imprinting strategy and ratio strategy, the MIP-RECS has impressive selectivity compared with the non-imprinted polymer-RECS, and has better repeatability and reproducibility than non-ratiometric sensor. The MIP-RECS has high sensitivity and accuracy, which was applied for the detection of OFL in four different brands of milk and was verified by HPLC method with satisfactory results.

Functionalized nano cellulose double-template imprinted aerogel microsphere for the targeted enrichment of taxanes

Paclitaxel, a diterpenoid isolated from the bark of Taxus wallichiana var. chinensis (Pilger) Florin, is currently showing significant therapeutic effects against a variety of cancers. Baccatin III (Bac) and 10-Deacetylbaccatin III (10-DAB) are in great demand as important precursors for the synthesis of paclitaxel. This work aims to develop a simple, rapid and highly selective, safe, and non-polluting molecularly imprinted material for 10-DAB and Bac enrichment. In this study, we innovatively prepared molecularly imprinted materials with nanocellulose aerogel microspheres and 2-vinylpyridine (2-VP) as a bifunctional monomer, and 10-DAB and Bac as bis-template molecules. In particular, functionalized nanocellulose dual-template molecularly imprinted aerogel microsphere (FNCAG-DMIM) were successfully synthesized by the bifunctional introduction of functional nanocellulose aerogel microsphere (FNCAG) modified with Polyethyleneimine (PEI) as a carrier and functional monomer, which provided a large number of recognition sites for bimodal molecules. FNCAG-DMIM showed high specificity for 10-DAB and Bac specific assays. Under the optimal experimental conditions, the adsorption capacities of FNCAG-DMIM for 10-DAB and Bac reached 52.27 mg g−1 and 53.81 mg g−1, respectively. In addition, it showed good reliability and practicality in the determination of real samples. The present study extends the research on the synthesis of natural functional monomers by molecularly imprinted materials and opens up new horizons for the targeted isolation of plant compounds by dual-template molecularly imprinted materials.

Synthesis of Cu and Zr-based coordination polymers with N/O donors and investigation of their photocatalytic activity against dye

The coordination polymers (CPs) of Cu and Zr were synthesized by the hydrothermal method. The orotic acid potassium salt (H3KL) was used as a linker, which coordinates via O–O. Whereas, 4,4′-trimethylenedipyridine (4,4′-TMDP) was used as a bifunctional monomer, which coordinates via N–N. The synthesized CPs were characterized by FTIR, P-XRD, TGA, DSC and SEM. The photocatalytic activity was investigated against methylene blue (MB) under sunlight irradiation. Both Cu-CP and Zr-CP exhibited potential activity for the degradation of MB, which was 72 % for Cu-CP and 93 % for Zr-CP. The band gap of the CPs was also investigated, and the observed value was 2.2 eV. The band gap indicates that these compounds could bring breakthroughs as photocatalysts instead of semiconductors. These kinds of CPs could be used for multiple purposes in industry and in a green environment.

A magnetically fixed bifunctional monomer molecularly imprinted electrochemiluminescence sensor for specifically identifying thiabendazole in food

A magnetically fixed bifunctional monomer molecularly imprinted electrochemiluminescence (ECL) sensor (MIP/MMOF@g-C3N4/L-Aas/MGCE) was constructed to selective detection thiabendazole (TBZ). Fe3O4 modified by sulfonic acid group (–SO3H) acted as magnetic core to attract Co2+ to initiate the growth of ZIF-67 (MMOF). Graphitic carbon nitride nanosheets (g-C3N4) were doped into MMOF by inherent amino groups to prepare integrated magnetic ECL luminophore (MMOF@g-C3N4). MMOF@g-C3N4 was immobilized on the surface of magnetic glassy carbon electrode (MGCE) by using the superparamagnetism of Fe3O4, which enhanced the stability and reusability of ECL system. Sodium ascorbate (L-Aas) acted as co-reactant accelerators to further enhance ECL intensity. MIP prepared with TBZ as template molecule and o-phenylenediamine (oPD)/resorcinol (RS) as bifunctional monomers contained more imprinting sites, which can enhance the adsorption performance. The luminescence mechanism of magnetic ECL system was investigated, and the specific recognition mechanism of MIP recognition system was deeply explored. The linear range of the method was 1 × 10−9–5 × 10−5 mol L−1, and the detection limit was 3.77 × 10−10 mol L−1. A good recovery rate (80.08%–96.82%) was obtained in the actual sample detection, which was basically consistent with the detection results of High Performance Liquid Chromatography.

Core-shell magnetic molecularly imprinted polymers prepared by self-polymerization of bifunctional monomers for efficient enrichment and separation of chloramphenicol in water samples

Chloramphenicol (CAP) is a potent antibiotic used to treat infections in livestock and humans, but its residues can be hazardous to human health. In this study, amino-modified Fe3O4 nanoparticles were prepared by a single-pot method, and magnetic molecularly imprinted materials were prepared by self-polymerization for imprinting with CAP. The imprinted thin layer was prepared by polymerization of dopamine (DA) and 3-aminophenylboronic acid (APBA) copolymers, which improved the elution efficiency of the template. Dopamine generated under alkaline conditions replaces the crosslinker and can be adsorbed on the surface of magnetic carriers. The aromatic groups in dopamine make it difficult to degrade and fall off after adsorption on the magnetic carrier surface. The maximum adsorption amount of CAP on magnetic materials was 6.5 mg/g. After several adsorption cycles, the CAP-MMIPs still had good stability. The results showed that the method can both specifically recognize and enrich the separation of the target antibiotics, which greatly reduced the pretreatment time of the samples and provided a new approach for the pretreatment of CAP.

ARGET-ATRP-Mediated Grafting of Bifunctional Polymers onto Silica Nanoparticles Fillers for Boosting the Performance of High-Capacity All-Solid-State Lithium-Sulfur Batteries with Polymer Solid Electrolytes.

The shuttle effect in lithium-sulfur batteries, which leads to rapid capacity decay, can be effectively suppressed by solid polymer electrolytes. However, the lithium-ion conductivity of polyethylene oxide-based solid electrolytes is relatively low, resulting in low reversible capacity and poor cycling stability of the batteries. In this study, we employed the activator generated through electron transfer atom transfer radical polymerization to graft modify the surface of silica nanoparticles with a bifunctional monomer, 2-acrylamide-2-methylpropanesulfonate, which possesses sulfonic acid groups with low dissociation energy for facilitating Li+ migration and transfer, as well as amide groups capable of forming hydrogen bonds with polyethylene oxide chains. Subsequently, the modified nanoparticles were blended with polyethylene oxide to prepare a solid polymer electrolyte with low crystallinity and high ion conductivity. The resulting electrolyte demonstrated excellent and stable electrochemical performance, with a discharge-specific capacity maintained at 875.2 mAh g-1 after 200 cycles.

Self‐Adaptive Aromatic Cation‐π Driven Dimensional Polymorphism in Supramolecular Polymers for the Photocatalytic Oxidation and Separation of Aromatic/Cyclic Aliphatic Compounds

AbstractThe phenomenon of polymorphism is ubiquitous in nature, the controlled manipulation of which not only increases our ontological understanding of nature but also facilitates the conceptualization and realization of novel functional materials. However, achieving targeted polymorphism in supramolecular assemblies (SAs) remains a formidable challenge, largely because of the constraints inherent in controlling the specific binding motifs of noncovalent interactions. Herein, we propose self‐adaptive aromatic cation‐π binding motifs to construct polymorphic SAs in both the solid and solution states. Using distinct discrete cation‐π‐cation and long‐range cation‐π binding motifs enables control of the self‐assembly directionality of a C2h‐symmetric bifunctional monomer, resulting in the successful formation of both two‐dimensional and three‐dimensional crystalline SAs (2D‐CSA and 3D‐CSA). The differences in the molecular packing of 3D‐CSA compared with that of 2D‐CSA significantly improve the charge separation and carrier mobility, leading to enhanced photocatalytic activity for the aerobic oxidation of thioanisole to methyl phenyl sulfoxide (yield of 99 % vs 57 %). 2D‐CSA, which has a vertical extended structure with favorable stronger interaction with toluene though face‐to‐face cation‐π interactions than methylcyclohexane, shows higher toluene/methylcyclohexane separation efficiency than 3D‐CSA (96.9 % for 2D‐CSA vs 56.3 % for 3D‐CSA).