Tunable Fluorine-Functionalized Scholl-Coupled Microporous Polymer for the Selective Adsorption and Ultrasensitive Analysis of Environmental Liquid-Crystal Monomers.

Liquid-crystal monomers (LCMs), especially fluorinated biphenyls and analogues (FBAs), are identified to be an emerging generation of persistent organic pollutants. However, there is a dearth of information about their occurrence and distribution in environmental water and lacustrine soil samples. Herein, a series of fluorine-functionalized Scholl-coupled microporous polymers (FSMP-X, X = 1-3) were designed and synthesized for the highly efficient and selective enrichment of FABs. Their hydrophobicity, porosity, chemical stability, and adsorption performance (capacity, rate, and selectivity) were regulated preciously. The best-performing material (FSMP-2) was employed as the on-line fluorous solid-phase extraction (on-line FSPE) adsorbent owing to its high adsorption capacity (313.68 mg g-1), fast adsorption rate (1.05 g h-1), and specific selectivity for FBAs. Notably, an enrichment factor of up to 590.2 was obtained for FSMP-2, outperforming commercial C18 (12.6-fold). Also, the underlying adsorption mechanism was uncovered by density functional theory calculations and experiments. Based on this, a novel and automated on-line FSPE-high-performance liquid chromatography method was developed for ultrasensitive (detection limits: 0.0004-0.0150 ng mL-1) and low matrix effect (73.79-113.3%) determination of LCMs in lake water and lacustrine soils. This study offers new insight into the highly selective quantification of LCMs and the first evidence for their occurrence and distribution in these environmental samples.

Ultra-Thin 2D Ionic Salt Supported with Strong Hydrogen-Bonding Assisted Ionic Interaction.

2D materials have attracted great interest since the report of graphene. However, because of the fragile stability of ultra-thin nanosheets, most studies are restricted to sheets maintained by strong covalent or coordination bonds. The research on which kind of bonds can maintain the free-standing existence of 2D nanosheets is still of great significance. Recently, 2D ionic salts are successfully synthesized on substrates, but whether 2D ionic salts can free-stand is still a problem. Herein this problem is addressed by a free-standing 2D ionic salt (thickness: ≈2 nm) exfoliated from a 4,4'-bipyridinium hydrochloride salt crystal. The stability of this 2D salt is supported by a strong NH···Cl hydrogen (H)-bonding assisted ionic interaction (17.99 kcal mol-1 ), which is verified by density functional theory calculation and natural bond orbital analysis. The salt crystal has strong air-stable radicals inside and the 2D ionic salt exhibits red fluorescence in solution and in solid-state, especially in solution the stokes shifts are very large (≈ 386 nm). This breakthrough work is not only beneficial for the construction of novel 2D materials but also for the understanding of H-bonding interactions.

Reconstruction of Highly-Defective MgO and Exceptional Photochemical Activity on CO2 Upgrade in Aqueous Solution.

Defects on metal oxide have attracted extensive attention in photo-/electrocatalytic CO2 reduction. Herein, porous MgO nanosheets with abundant oxygen vacancies (Vo s) and three-coordinated oxygen atoms (O3c ) at corners are reported, which reconstruct into defective MgCO3 ·3H2 O exposing rich surface unsaturated -OH groups and vacancies to initiate photocatalytic CO2 reduction to CO and CH4 . In consecutive 7-cycle tests (each run for 6 h) in pure water, CO2 conversion keeps stable. The total production of CH4 and CO attains ≈367 µmol gcata -1 h-1 . The selectivity of CH4 gradually increases from ≈3.1% (1st run) to ≈24.5% (4th run) and then remains unchanged under UV-light irradiation. With triethanolamine (3.3 vol.%) as the sacrificial agent, the total production of CO and CH4 production rapidly increases to ≈28 000 µmol gcata -1 in 2 h reaction. Photoluminescence spectra reveal that Vo s induces the formation of donor bands to promote charge carrier seperation. A series of trace spectra and theoretical analysis indicate Mg-Vo sites in the derived MgCO3 ·3H2 O are active centers, which play a crucial role in modulating CO2 adsorption and triggering photoreduction reactions. These intriguing results on defective alkaline earth oxides as potential photocatalysts in CO2 conversion may spur some exciting and novel findings in this field.

Designing Hierarchically Porous Single Atoms of Fe-N5 Catalytic Sites with High Oxidase-like Activity for Sensitive Detection of Organophosphorus Pesticides.

Recently, single-atom catalysts (SACs) have been used to construct biosensors for the determination of organophosphorus pesticides (OPs). However, most nanozymes including SACs are peroxidase-like enzymes and require highly toxic and unstable hydrogen peroxide (H2O2) as a co-reactant to generate reactive oxygen species. Inspired by the heme site of cytochrome c oxidases (Ccos), the construction of Fe-N5-coordinated SACs by introducing axial N ligands is expected to bind O2 to generate active metal-oxygen intermediates. Herein, a SAC with an Fe-N5 active center confined by hierarchically porous carbon nanoframes (Fe SAs/N5-pC-4) was prepared by a polymerization-pyrolysis-evaporation-etching strategy, and its underlying enzyme-like mechanism was uncovered through experiments and density functional theory calculations. The 100% metal atom utilization, increased accessible active sites, accelerated mass transfer, excellent hydrophilicity, and an electron-driven mechanism of axial N endow the SAC with enhanced oxidase-like activity. Notably, its catalytic rate constant (0.398 s-1) is 569 times greater than that of the commercial Pt/C catalyst. Similar to the catalytic mechanism of Ccos, O2 can be converted into reactive oxygen species, avoiding the use of co-reactant H2O2 effectively. In addition, based on the inhibitory effect of thiols on the active site of Fe SAs/N5-pC-4, a biosensor was constructed and applied to the colorimetric analysis of OPs. This provides a facile, cost-effective method for efficient OP screening at sites to help control their contamination.

N-Methylquinuclidinium-Based Anion Exchange Membrane with Ultrahigh Alkaline Stability.

Anion-exchange-membrane (AEM) water electrolysis is a promising technology for hydrogen production from renewable energy sources. However, the bottleneck of its development is the poor comprehensive performance of AEM, especially the stability at highly concentrated alkaline condition and temperature. Herein, a new cationic group N-methylquinuclidinium with enhanced alkaline stability is proposed and hereby a full-carbon chain poly(aryl quinuclidinium) AEM is prepared. Compared with reported AEMs, it shows ultrahigh comprehensive alkaline stability (no chemical decomposition, no decay of conductivity) in 10 m NaOH aqueous solution at 80 °C for more than 1800 h, excellent dimensional stability (swelling ratio: <10% in pure water, <2% in 10 m NaOH) in OH- form at 80 °C, high OH- conductivity (≈139.1 mS cm-1 at 80 °C), and high mechanical properties (tensile strength: 41.5 MPa, elongation at break: 50%). The water electrolyzer using the AEM exhibits a high current density (1.94 A cm-2 at 2.0 V) when assembled with nickel-alloy foam electrodes, and high durability when assembled with nickel foam electrodes.

Construction of continuous flow catalytic reactor-HPLC system with ultrahigh catalytic activity using 2D nanoflower MOF-derived Cu2O/Cu/PDA/CF catalyst.

Currently, metal-organic frameworks (MOFs) derived materials have been widely concerned for the reduction of 4-nitrophenol (4-NP). However, complex recovery of powder catalysts and low utilization ratio of active sites make their application challenging. Herein, a novel Cu2O/Cu/PDA/CF catalyst has been developed for the rapid reduction of 4-NP to 4-aminophenol (4-AP). The catalyst was constructed by compositing a two-dimensional nanoflower MOF-derived nanoporous Cu2O/Cu network on a polydopamine (PDA)-modified porous copper foam by a mild and controllable in-situ reduction synthesis. Notably, an enhanced catalytic performance of Cu2O/Cu/PDA/CF was obtained for 4-NP reduction with a rate constant (k) of 0.8001 min-1, outperforming Cu/PDA/CF-X (X = 400, 500 and 600 â„ƒ pyrolysis temperature) catalysts (2.3-6.4 folds), and even many reported catalysts (2.3-46.5 folds). The ultrafast degradation of 4-NP was completed in 70 s. Moreover, an ingenious online continuous flow catalytic reactor (CFCR)-high performance liquid chromatography (HPLC) system was constructed for automatic and real-time monitoring of the reduction reaction. System stability experiments over 300 min revealed a surprisingly high reaction k value of 76.68 min-1 at low NaBH4 usage, significant increasing by 2-3 orders of magnitude compared with Cu2O/Cu/PDA/CF batch catalysis, due to the high aspect ratio of 2D nanoflower MOF and convection-accelerated mass transfer. This work offers new insights for the rational design of catalytic reactor and its potential application in wastewater treatment.

Development of an online µ-matrix cartridge extraction method for fipronil extraction in contaminated soils.

Nowadays, environment fate and behavior of pesticides in soil is still not fully understood due to the lack of standardized soil extraction method. In this work, a soil-filled micro-matrix cartridge was online combined with high performance liquid chromatography-mass spectrometry (HPLC-MS) through a six-way valve for the simultaneous extraction and determination of residual fipronil in soil. Compared with conventional extraction methods, such as hydroxypropyl-ß-cyclodextrin (HPCD) extraction, shaking extraction, ultrasonic-assisted extraction (UAE), three-step extraction and matrix solid phase dispersion (MSPD), the novel, miniaturized, and integrated online micro-matrix cartridge extraction (online µ-MCE) method exhibited better performance in terms of desorption efficiency (99.4%), analysis time, solvent consumption, sensitivity, and automation. In sequential extraction, online µ-MCE could further desorb fipronil from the extracted soil with the percentage of 1.05%-58.55%. High recovery of 92.69% obtained for the ISO certificated test-soil verified the satisfactory accuracy of the method. Besides, its wide universality was also validated in three variables: 1) various pesticides-soil interactions, 2) four types of compounds (aromatic hydrocarbons, carboxylic acids, alcohols and aldehydes), and 3) three types of soils (sandy soil, silty loam and silty clay). The superior desorption capacity might be attributed to the instantaneously increased high-pressure, continuous flow dynamic desorption and short residence time. The present encouraging findings might shed light on new ways to develop a mild, highly efficient, reliable and one-fit-all extraction method toward pesticide contaminated soil.

A novel solid-phase microextraction method based on polymer monolith frit combining with high-performance liquid chromatography for determination of aldehydes in biological samples.

In this work, a polypropylene frit with porous network structure (20 µm pole size) was first utilized as the mould of polymer monolithic material, poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MAA-co-EDMA) monolith was synthesized within channels and macropores of the frit. A simple and sensitive solid-phase microextraction method based on polymer monolith frit coupled with high-performance liquid chromatography (HPLC) was established and applied to analysis of hexanal and heptanal in biological samples (human urine and serum). In the method, small molecule metabolites (aldehydes) in biological samples derivatized with 2,4-dinitrophenylhydrazine (DNPH), and the formed hydrazones were extracted simultaneously on the monolithic frit and thereafter ultrasound-assisted desorbed with acetonitrile as elution solvent. The experimental parameters with regard to polymerization, derivatization and extraction were investigated. Under the optimal conditions, the linearity was in the range of 0.02-5.0 µmol L(-1) (r=0.9994) for both hexanal and heptanal and the limits of detection (S/N=3) were 0.81 nmol L(-1) for hexanal and 0.76 nmol L(-1) for heptanal. The relative standard deviations (RSDs, n=5) were less than 6.5% for the same monolithic frit and less than 8.9% for the different monolithic frits. Satisfactory recoveries ranging from 70.71% to 88.73% were obtained for the urine samples. The method possesses many advantages including simple setup, fast analysis, low cost, sufficient sensitivity, good biological compatibility and less organic solvent consumption. The proposed method is a useful assistant tool in the clinical early diagnosis of lung disease by monitoring aldehyde biomarker candidates in complex biological samples.

Analysis of volatile aldehyde biomarkers in human blood by derivatization and dispersive liquid-liquid microextraction based on solidification of floating organic droplet method by high performance liquid chromatography.

A new dispersive liquid-liquid microextraction based on solidification of floating organic droplet method (DLLME-SFO) was developed for the determination of volatile aldehyde biomarkers (hexanal and heptanal) in human blood samples. In the derivatization and extraction procedure, 2,4-dinitrophenylhydrazine (DNPH) as derivatization reagent and formic acid as catalyzer were injected into the sample solution for derivatization with aldehydes, then the formed hydrazones was rapidly extracted by dispersive liquid-liquid microextraction with 1-dodecanol as extraction solvent. After centrifugation, the floated droplet was solidified in an ice bath and was easily removed for analysis. The effects of various experimental parameters on derivatization and extraction conditions were studied, such as the kind and volume of extraction solvent and dispersive solvent, the amount of derivatization reagent, derivatization temperature and time, extraction time and salt effect. The limit of detections (LODs) for hexanal and heptanal were 7.90 and 2.34nmolL(-1), respectively. Good reproducibility and recovery of the method were also obtained. The proposed method is an alternative approach to the quantification of volatile aldehyde biomarkers in complex biological samples, being more rapid and simpler and providing higher sensitivity compared with the traditional dispersive liquid-liquid microextraction (DLLME) methods.