Ozone-Induced Rapid and Green Synthesis of Polydopamine Coatings with High Uniformity and Enhanced Stability.

The development of green, controllable, and simplified pathways for rapid dopamine polymerization holds significant importance in the field of polydopamine (PDA) surface chemistry. In this study, a green strategy is successfully devised to accelerate and control the polymerization of dopamine through the introduction of ozone (O3 ). The findings reveal that ozone serves as an eco-friendly trigger, significantly accelerating the dopamine polymerization process across a broad pH range, spanning from 4.0 to 10.0. Notably, the deposition rate of PDA coatings on a silicon wafer reaches an impressive value of ≈64.8 nm h-1 (pH 8.5), which is 30 times higher than that of traditional air-assisted PDA and comparable to the fastest reported method. Furthermore, ozone exhibits the ability to accelerate dopamine polymerization even under low temperatures. It also enables control over the inhibition-initiation of the polymerization process by regulating the "ON/OFF" mode of the ozone gas. Moreover, the ozone-induced PDA coatings demonstrate exceptional characteristics, including high homogeneity, good hydrophilicity, and remarkable chemical and mechanical stability. Additionally, the ozone-induced PDA coatings can be rapidly and effectively deposited onto a wide range of substrates, particularly those that are adhesion-resistant, such as polytetrafluoroethylene (PTFE).

Design and Synthesis of Low Dielectric Poly(aryl ether ketone) from Incorporation Bulky Fluorene Groups and Regular Hydroquinone Structure.

To decrease the dipole polarization rate and reduce the dielectric constant of poly(aryl ether ketone) (PAEK) resin, 1,4-di(4-fluorobenzoyl) cyclohexane (DFBCH), a weakly polarizing cyclohexane-based monomer, was designed and synthesized as the primary reactant. The bulky fluorene group was incorporated to increase the free volume of the resin, further reducing the dielectric constant. Additionally, hydroquinone with a symmetric and regular structure was utilized to enhance the molecular chain's regularity and reduce dipole relaxation, further lowering the resin's dielectric constant and dielectric loss. The PFQEKs series resins exhibited excellent thermal stability with glass transition temperature (Tg) ranging from 222 to 239 °C and 5% weight loss (Td5%) ranging from 458 to 463 °C, with different monomer ratios. As the hydroquinone content increased, the dielectric constant (Dk) and dielectric loss (Df) of the resin decreased significantly, with Dk ranging from 2.92 to 2.77 and Df ranging from 0.011 to 0.008 at 10 GHz.

Non-Coplanar Diphenyl Fluorene and Weakly Polarized Cyclohexyl Can Effectively Improve the Solubility and Reduce the Dielectric Constant of Poly (Aryl Ether Ketone) Resin.

With the rapid development of high-frequency communication and large-scale integrated circuits, insulating dielectric materials require a low dielectric constant and dielectric loss. Poly (aryl ether ketone) resins (PAEK) have garnered considerable attention as an intriguing class of engineering thermoplastics possessing excellent chemical and thermal properties. However, the high permittivity of PAEK becomes an obstacle to its application in the field of high-frequency communication and large-scale integrated circuits. Therefore, reducing the dielectric constant and dielectric loss of PAEK while maintaining its excellent performance is critical to expanding the PAEK applications mentioned above. This study synthesized a series of poly (aryl ether ketone) resins that are low dielectric, highly thermally resistant, and soluble, containing cyclohexyl and diphenyl fluorene. The effects of cyclohexyl contents on the properties of a PAEK resin were studied systematically. The results showed that weakly-polarized cyclohexyl could reduce the molecular polarization of PAEK, resulting in low permittivity and high transmittance. The permittivity of PAEK is 2.95-3.26@10GHz, and the transmittance is 65-85%. In addition, the resin has excellent solubility and can be dissolved in NMP, DMF, DMAc, and other solvents at room temperature. Furthermore, cyclohexyl provided PAEK with excellent thermal properties, including a glass transition temperature of 239-245 °C and a 5% thermogravimetric temperature, under a nitrogen atmosphere of 469-534 °C. This makes it a promising candidate for use in high-frequency communications and large-scale integrated circuits.

One-pot synthesis of hierarchical Co1-xS/NC@MoS2/C hollow nanofibers based on one-dimensional metal coordination polymers for enhanced lithium and sodium-ion storage.

Multicomponent metal sulfides have been recognized as promising anode materials for lithium/sodium-ion storage given their enticing theoretical capacities. However, the simplification of synthetic processes and the construction of heterogeneous interfaces of multimetal sulfides remain great challenges. Herein, a hierarchical 1T-MoS2/carbon nanosheet decorated Co1-xS/N-doped carbon (Co1-xS/NC@MoS2/C) hollow nanofiber was designed and constructed via a one-pot hydrothermal method using a cobalt-based coordination polymer nanofiber. This nanofiber can transform in-situ into conductive N-doped carbon hollow fibers embedded with active Co1-xS nanoparticles, enabling the epitaxial growth of MoS2 nanosheets. Consequently, the Co1-xS/NC@MoS2/C composites achieve exceptional lithium/sodium-ion storage performance. Compared to MoS2/C microspheres and Co1-xS/NC hollow nanofibers alone, the Co1-xS/NC@MoS2/C hollow nanofibers deliver higher discharge capacities (1085.9 mAh g-1 for lithium-ion batteries (LIBs) and 748.5 mAh g-1 for sodium-ion batteries (SIBs) at 100 mA g-1), better capacity retention (910 mAh g-1 for LIBs and 636.5 mAh g-1 for SIBs after 150 cycles at 100 mA g-1), and increased cycling stability (407.2 mAh g-1 after 1000 cycles for SIBs at 1000 mA g-1). Furthermore, the kinetic analysis shows that the lithium/sodium-ion storage processes of the Co1-xS/NC@MoS2/C electrode are mainly controlled by pseudocapacitance behavior. The excellent electrochemical properties can thus be ascribed to the synergy of the MoS2/C nanosheets with the enlarged interlayer spacing, good conductivity of the carbon layers, and the Co1-xS nanoparticles embedded in the hollow nanofibers with extensive reaction sites.

A Conductive and Highly Deformable All-Pseudocapacitive Composite Paper as Supercapacitor Electrode with Improved Areal and Volumetric Capacitance.

Flexible energy storage electronics have gained increasing attention in recent years, but the simultaneous acquiring of high volumetric and high areal capacities as well as excellent flexibility in order to truly implement wearable and portable electronics in practice remains challenging. Here, a conductive and highly deformable freestanding all-pseudocapacitive paper electrode (Ti3 C2 Tx /MnO2 NWs) is fabricated by solution processing of hybrid inks based on Ti3 C2 Tx MXene and ultralong MnO2 nanowires. The resulting Ti3 C2 Tx /MnO2 NWs hybrid paper manifests a remarkable areal capacitance of up to 205 mF cm-2 and outstanding volumetric capacitance of 1025 F cm-3 . Both the values are highly comparable with, or in most cases much higher than those of previously reported MXene-based flexible electrodes. The excellent energy storage performance is well maintained with a capacitance retention of 98.38% during 10 000 charge-discharge cycles. In addition, the flexible supercapacitor demonstrates excellent flexibility and electrochemical stability during repeated mechanical bendings of up to 120°, suggesting great potentials for the applications in future flexible and portable electronics.

SnS2 Nanosheets Coating on Nanohollow Cubic CoS2 /C for Ultralong Life and High Rate Capability Half/Full Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have attracted tremendous interest and become a worldwide research hotpot owing to their low cost and abundant resources. To obtain suitable anode materials with excellent performance for SIBs, an effective and controllable strategy is presented to fabricate SnS2 nanosheets coating on nanohollow cubic CoS2 /C (CoS2 /C@SnS2 ) composites with a hollow structure using Co-metal-organic frameworks as the starting material. As anodes for SIBs, the CoS2 /C@SnS2 electrode exhibits ultralong cycle life and excellent rate performance, which can maintain a high specific capacity of 400.1 mAh g-1 even after 3500 cycles at a current density of 10 A g-1 . When used in a full-cell, it also shows enhanced sodium storage properties and delivers a high reversible capacity of 567.3 mAh g-1 after 1000 cycles at 1 A g-1 . This strategy can pave a way for preparing various metal sulfides with fascinating structure and excellent performance for the potential application in energy storage area.

Determination of chlorophenols in water using dispersive liquid-liquid microextraction coupled with water-in-oil microemulsion electrokinetic chromatography in normal stacking mode.

The current routes to couple dispersive liquid-liquid microextraction with capillary electrophoresis are the evaporation of water immiscible extractants and the back-extraction of analytes. In this study, a new methodology for this combination using water-in-oil microemulsion electrokinetic chromatography coupled with normal stacking mode on-line sample concentration was developed to analyze chlorophenols in water samples. The analytes were extracted with tributyl phosphate and the extractant dilution (3×) was directly injected into an electrophoresis buffer (7.7 cm) containing 5% sodium dodecyl sulfate, 78% 1-butanol, 2% 1-heptane, and 15% sodium acetate solution (pH 8.0). This proposed method is very simple and convenient compared to the conventional procedures. The key parameters affecting separation and concentration were systematically optimized. Under the optimized conditions, dispersive liquid-liquid microextraction contributed an enrichment factor of 45-50, and the overall sensitivity improvement was 312-418-fold. Limits of detection between 1.4 and 3.0 ng/mL and limits of quantification between 4.5 and 10.2 ng/mL were achieved. Acceptable repeatability lower than 3.0% for migration time and 9.0% for peak areas were obtained. The developed method was successfully applied for analysis of the chlorophenols in real water samples.

Determination of benzo[a]pyrene in edible oils using phase-transfer-catalyst-assisted saponification and supramolecular solvent microextraction coupled to HPLC with fluorescence detection.

For the analysis of edible oils, saponification is well known as a useful method for eliminating oil matrices. The conventional approach is conducted with alcoholic alkali; it consumes a large volume of organic solvents and impedes the retrieval of analytes by microextraction. In this study, a low-organic-solvent-consuming method has been developed for the analysis of benzo[a]pyrene in edible oils by high-performance liquid chromatography with fluorescence detection. Sample treatment involves aqueous alkaline saponification, assisted by a phase-transfer catalyst, and selective in situ extraction of the analyte with a supramolecular solvent. Comparison of the chromatograms of the oil extracts obtained by different microextraction methods showed that the supramolecular solvent has a better clean-up effect for the unsaponifiable matter from oil matrices. The method offered excellent linearity over a range of 0.03- 5.0 ng mL-1 (r > 0.999). Recovery rates varied from 94 to 102% (RSDs <5.0%). The detection limit and quantification limit were 0.06 and 0.19 µg kg-1 , respectively. The proposed method was applied for the analysis of 52 edible oils collected online in China; the analyte contents of 23 tested oil samples exceeded the maximum limit of 2 µg kg-1 for benzo[a]pyrene set by the Commission Regulation of the European Union.

Study of the mechanism of acetonitrile stacking and its application for directly combining liquid-phase microextraction with micellar electrokinetic chromatography.

Acetonitrile stacking is an online concentration method that is distinctive due to its inclusion of a high proportion of organic solvent in sample matrices. We previously designed a universal methodology for the combination of liquid-phase microextraction (LPME) and capillary electrophoresis (CE) using acetonitrile stacking and micellar electrokinetic chromatography (MEKC) mode, thereby achieving large-volume injection of the diluted LPME extractant and the online concentration. In this report, the methodology was extended to the analysis of highly substituted hydrophobic chlorophenols in wines using diethyl carbonate as the extractant. Additionally, the mechanism of acetonitrile stacking was studied. The results indicated that the combination of LPME and MEKC exhibited good analytical performance: with ∼40-fold concentration by LPME, a 20-cm (33% of the total length) sample plug injection of an eight-fold dilution of diethyl carbonate with the organic solvent-saline solution produced enrichments higher by a factor of 260-791. Limits of qualification ranged from 5.5 to 16.0ng/mL. Acceptable reproducibilities of lower than 1.8% for migration time and 8.6% for peak areas were obtained. A dual stacking mechanism of acetonitrile stacking was revealed, involving transient isotachophoresis plus pH-junction stacking. The latter was associated with a pH shift induced by the presence of acetonitrile. The pseudo-stationary phase (Brij-35) played an important role in reducing the CE running time by weakening the isotachophoretic migration of the analyte ions following Cl(-) ions. The combination of acetonitrile stacking and nonionic micelle-based MEKC appears to be a perfect match for introducing water-immiscible LPME extractants into an aqueous CE system and can thus significantly expand the application of LPME-CE in green analytical chemistry.