Fluorine-Containing Covalent Organic Frameworks: Synthesis and Application.

Covalent organic frameworks (COFs) are a type of crystalline porous polymers that possess ordered structures and eternal pores. Because of their unique structural characteristics and diverse functional groups, COFs have been used in various application fields, such as adsorption, catalysis, separation, ion conduction, and energy storage. Among COFs, the fluorine-containing COFs (fCOFs) have been developed for special applications by virtue of special physical and chemical properties resulting from fluorine element, which is a nonmetallic halogen element and possesses strong electronegativity. In the organic chemistry field, introducing fluorine into chemicals enables those chemicals to exhibit many interesting properties, and fluorine chemistry increasingly plays an important role in the history of chemical development. The introduction of fluorine in COFs can enhance the crystallinity, porosity, and stability of COFs, making COFs having superior performances and some new applications. In this review, the synthesis and application of fCOFs are systematically summarized. The application involves photocatalytic production of hydrogen peroxide, photocatalytic water splitting, electrocatalytic CO2 reduction, adsorption for different substances (H2 , pesticides, per-/polyfluoroalkyl substances, polybrominated diphenyl ethers, bisphenols, and positively charged organic dye molecules), oil-water separation, energy storage (e.g., zinc-ion batteries, lithium-sulfur batteries), and proton conduction. Perspectives of remaining challenges and possible directions for fCOFs are also discussed.

Effects of different concentrations of sodium hypochlorite on dentine adhesion and the recovery application of sodium erythorbate. / ä¸åŒæµ“åº¦æ¬¡æ°¯é ¸é’ å¤„ç†å¯¹ç‰™æœ¬è´¨ç²˜æŽ¥çš„å½±å“åŠå¼‚æŠ—åè¡€é ¸é’ çš„æ¢å¤ä½œç”¨.

OBJECTIVES: Root canal therapy is the most effective and common method for pulpitis and periapical periodontitis. During the root canal preparation, chemical irrigation plays a key role. However, sodium hypochlorite (NaOCl), the widely used irrigation fluid, may impact the bonding strength between dentin and restorative material meanwhile sterilization and dissolving. Therefore, it's important to explore the influence of NaOCl on the adhesion between dentin and restoration materials to ensure clinical efficacy. This study aims to explore the effect of NaOCl on dentine adhesion and evaluate the effect of dentine adhesion induced by sodium erythorbate (ERY), and to provide clinical guidance on dentin bonding after root canal therapy. METHODS: Seventy freshly complete extracted human third molars aged 18-33 years old, without caries and restorations were selected. A diamond saw was used under running water to achieve dentine fragments which were divided into 10 groups with 14 fragments in each group: 2 control [deionized water (DW)±10% ERY] and 8 experimental groups (0.5%, 1%, 2.5%, and 5.25% NaOCl±10% ERY). The dentine specimens in the control group (treated with DW) and the experimental groups (treated with 0.5% NaOCl, 1% NaOCl, 2.5% NaOCl, and 5.25% NaOCl) were immersed for 20 min using corresponding solutions which were renewed every 5 min. The other 5 groups were immersed in 10% ERY for 5 min after an initial washing with DW for 1 min. Then, we selected 4 dentine fragments from all 14 fragments in each group and the numbers and diameters of opening dentinal tubules were observed under scanning electron microscope (SEM). The other 10 dentine fragments from each group were used to make adhesive samples by using self-etch adhesive wand composite resin. All the above adhesive samples were sectioned perpendicular to the bonded interface into 20 slabs with a cross-sectional area of 1 mm×1 mm using a diamond saw under the cooling water, and then the morphology of 10 slabs in each group's bonding interface was observed from aspects of formation of resin tags, depth of tags in dentin, and formation of hybrid layer under SEM. The other 10 slabs of each group's microtensile bond strength and failure modes were also analyzed. RESULTS: Among the 0.5% NaOCl, 1% NaOCl, 2.5% NaOCl, and 5.25% NaOCl groups, the number and diameter of patent dentinal tubules gradually increased with the rise of concentration of NaOCl solution (all P<0.05). Among the DW, 0.5% NaOCl, 1% NaOCl, 2.5% NaOCl, and 5.25% NaOCl groups, the number and diameter of patent dentinal tubules increased after using ERY, but without significant difference (all P>0.05). Among the DW, 0.5% NaOCl, 1% NaOCl, and 2.5% NaOCl groups, the scores of formation of resin tags under SEM gradually increased with the increase of concentration of NaOCl solution, while the score in the 5.25% NaOCl group decreased significantly compared with the score of the 2.5% NaOCl group (P<0.05). There was no significant difference between using 10% ERY groups and without using 10% ERY groups (all P>0.05). The scores of length of the tags under SEM in the 5.25% NaOCl group was significantly higher than the scores of DW, 0.5% NaOCl, and 1% NaOCl groups (all P<0.05), and it was also higher than the score of the 2.5% NaOCl group, but without significant difference (P>0.05). There was no significant difference between using 10% ERY groups and without using 10% ERY groups (P>0.05). The scores of formation of hybrid layer under SEM in the 2.5% NaOCl and 5.25% NaOCl groups significantly decreased compared with the score of the DW group (all P<0.05). There were significant differences between the 2.5% NaOCl±10% ERY groups and between the 5.25% NaOCl±10% ERY groups (all P<0.05). Microtensile bond strength was greater in the 0.5% NaOCl, 1% NaOCl, and 2.5% NaOCl groups, but lower in the 5.25% NaOCl group than that in the DW group (all P<0.05). There were significant differences between the 2.5% NaOCl±10% ERY groups and between the 5.25% NaOCl±10% ERY groups (all P<0.05). The incidence of type "Adhesive" of failure modes in the 5.25% NaOCl group was significantly higher than that in other groups (all P<0.05), while the incidence of type "Adhesive" in the 5.25% NaOCl+10% ERY group was lower than that in the 5.25% NaOCl group (P<0.05). CONCLUSIONS: The bonding strength to dentine increases with the increase of NaOCl concentration when the concentration lower than 2.5%; whereas it is decreased at a higher concentration (such as 5.25%). 10% ERY has a definite recovery effect on attenuated bonding strength to 5.25% NaOCl-treated dentine.

Controlled assembly of inorganic-organic frameworks based on [SeMo6O21]4- polyanion.

The chemical system based on [SeMo6O21](4-) polyanion and carboxylate ligand has been investigated. According to the inherent nature of organic groups, a series of selenomolybdates with three architectures have been isolated through rational and deliberate synthetic routes by stereospecific addition of different carboxylic acids. Such an approach is potentially interesting for {SeMo6} cluster, which exhibits a high surface nucleophilicity and is capable of being functionalized by covalently bound carboxylic acids. Investigation of the assemblies reveals that carboxylic acids have good flexibility and conformational freedom, representing the powerful chemical tools to control the polyanion assembly processes.