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Uranium is an essential nuclear material in civilian and military areas; however, its extensive application raises concerns about the potential safety issues in the fields of environmental protection and nuclear industry. In this study, we developed an Ag/Ag2O-COF (covalent-organic framework) composite SERS substrate to detect uranyl ions (UO22+) in environmental aqueous solutions. Herein, the strong SERS effect of uranyl adsorbed in Ag/Ag2O composite and the high adsorption efficiency of COF TpPa-1 were combined to realize the trace detection of uranyl ions. This method displayed a linear range of 10-8 mol L-1 to 10-6 mol L-1 with the detection limit of 8.9 × 10-10 mol L-1 for uranyl ions. Furthermore, common metal cations and oxo-ions hardly affected the SERS detection of uranyl, which is helpful for the trace analysis of uranyl in natural water samples. Although the proposed strategy is deployed for uranyl detection, the reusable and high-efficiency system may be expanded to trace detection of other substance with Raman activity.

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Adsorptive removal of dyes (e.g., malachite green (MG)) from wastewater using commercially available adsorbents is not significantly efficient. Metal-organic frameworks (MOFs) such as Cu-BTC is considered as an excellent adsorbent in adsorption-separation filed. However, the water instability of Cu-BTC restricts its potential utilization in dye wastewater purification. In this paper, we have developed a novel metal/covalent-organic frameworks (Cu-BTC@TpPa-1) binary composite by solvothermal method. This composite serves as a multifunctional platform for the effective removal of MG from water. This Cu-BTC@TpPa-1 obviously keeps structural integrity soaked in water for 7 days. And its heat resistant performance can achieve 360 °C because of the TpPa-1 protection, which is outdistance to that of Cu-BTC. The adsorbed capacity of MG over Cu-BTC@TpPa-1 is exceptionally high, with an uptake of up to 64.12 mg/g, which is superior compared to previous adsorbents, highlighting its superior adsorption capabilities. The adsorptive performance was controlled by the associative effects of Cu-BTC and TpPa-1 with an association effect of π-complexation and electrostatic attraction. The Cu-BTC@TpPa-1 might be a prospective adsorbent for MG capture from industrial wastewater.

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Three synthesis procedures for the covalent-organic framework (COF) TpPa-1 are studied with the purpose of setting up the most promising one in a fast and green way, leading to a more environmentally friendly and sustainable process. With conventional heating, good crystallinity and a high BET specific surface area (SSA) of up to 1007 m2 ⋅ g-1 are achieved at 170 °C for 3 days using water as the quintessential green solvent. However, the application of microwave radiation in the synthesis for this crystalline porous polymer allows reaction times to be shortened to 30 min while maintaining structural and textural properties (BET SSA of 928 m2 ⋅ g-1 ) and obtaining yields close to 98 % (vs. 90 % in the hydrothermal synthesis). The water-assisted mechanochemical synthesis is also an environmentally friendly synthetic approach; with heating at 170 °C in a two-step process (10+10 min), high crystallinity is achieved, a BET SSA of 960  m2 ⋅ g-1 and a yield of 98 % for TpPa-1.

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It is a major challenge to combine the advantages of two kinds of two-dimensional materials to construct a heterojunction and achieve efficient photocatalytic antifouling. In this work, we covalently connected two materials MXenes and covalent organic frameworks (COFs) through the Schiff base reaction and anchored Ag nanoparticles (NPs) to prepare a Ti3C2/TpPa-1/Ag composite material with high efficiency bactericidal properties. The covalent bonding between MXene and COF greatly improved the stability of the material. Ti3C2/TpPa-1/Ag composite showed an excellent antibacterial property against S. aureus and P. aeruginosa. The fluorescence spectra of Ti3C2/TpPa-1/Ag proved that the electron transfer channels formed between the ternary materials could greatly improve the efficiency of carrier separation and prolong the life of photogenerated carriers. Density functional theory calculations showed that the synergistic catalytic effect of Ag and Ti3C2 could greatly reduce the work function along the interface, and the built-in electric field between the layers drive carrier fast migration, which effectively improve the catalytic performance.

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A simple and feasible strategy was developed for the preparation of fluorescent covalent organic frameworks (COFs) TpPa-1@FL. The TpPa-1-1@FL was prepared via a self-assembly strategy by soaking non-fluorescent COFs TpPa-1 into strong fluorescent fluorescein (FL) solution. A chemiluminescence resonance energy transfer (CRET) system was constructed by the combination strong fluorescent TpPa-1@FL with TCPO-hydrogen peroxide (H2O2) reaction. The chemiluminescence (CL) signal of the system was further improved by the addition of bovine serum albumin (BSA). The CRET system can determine H2O2 with a linear range response from 5.0 µmol/L to 20.0 mmol/L and a detection limit of 1.1 µmol/L. The CRET system was further exploited for indirect detection of uric acid with coupling of uricase. A good linear relationship was obtained for uric acid in the 10.0-400.0 µmol/L concentration range with a detection limit of 3.8 µmol/L. The practicability of this method was assessed by the determination of uric acid in real samples of human serum and urine.

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The binary nanocomposites of metal/covalent-organic frameworks (NH2-MIL-125(Ti)@TpPa-1) were constructed by solvothermal method, which was developed as a multifunctional platform with adsorption and photocatalysis for radionuclides removal. The batch experiments and physicochemical property (FT-IR, XRD, SEM, TEM, XPS, etc.) corroborated: (i) core-shell NH2-MIL-125(Ti)@TpPa-1 had a more stable, multilayer pore structure and abundant active functional groups; (ii) NH2-MIL-125(Ti)@TpPa-1 had fast a removal rate, as well as a high adsorption capacity of 536.73 mg (UO22+)/g and 593.97 mg (Eu3+)/g; (iii) the pseudo-second-order and Langmuir model provided a more reasonable description, indicating the immobilization process was endothermic, spontaneous chemisorption; (iv) the adsorption mechanism was chelation and electrostatic attraction, ascribed to the nitrogen/oxygen-containing functional groups. These results illustrated that NH2-MIL-125(Ti)@TpPa-1 was a prospective adsorbent for the remediation polluted by radionuclides. In addition, the research provided the theoretical basis for further investigation on the UO22+(VI) photoreduction.

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The secretion disorder of sex hormones is the source that leads to the occurrence of many diseases such as polycystic ovarian syndrome (PCOS), hyperandrogenism and so on. There exist physiological changes in human body when slight fluctuations in concentrations of sex hormones happen. Therefore, it's of great significance for accurate detection of sex hormones in human body. In this work, TpPa-1 COF solid-phase microextraction (SPME) fiber was prepared using high-efficient in-situ synthesis strategy and coupled with HPLC-MS/MS to detect three sex hormones, including Progesterone (P), testosterone (T) and dehydroepiandrosterone (DHEA) in human serum. The thickness of the coating reached 7 µm within 2 h. Under the optimal conditions, the established method presented low limit of detections (LODs, ≤ 0.75 ng/mL), wide linear ranges (0.100-100 ng mL-1) and good reproducibility, and three sex hormones (T, P, DHEA) were successfully detected and quantified in human serum. In conclusion, the established SPME method presented high-efficient fiber preparation and good analytical performances of sex hormone detection, therefore was in great potential for application in clinical.

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The magnetic covalent organic framework with ß-ketoenamine linkage (Fe3O4@COF(TpPa-1)) was fabricated by the hydrothermal method. The obtained Fe3O4@TpPa-1 integrated four advantages, namely easy preparation, high stability, excellent adsorption performance (485.2 m2/g) and good recoverability (19.5 emu/g), which enabled it an ideal sorbent for wastewater treatment. Fe3O4@TpPa-1 exhibited excellent adsorption capacities for Cr (VI) (245.45 mg/g) and bisphenol A (1220.97 mg/g). The adsorption kinetics and isotherms were in alignment to the pseudo-second-order and Langmuir model, respectively. After five times cycles, the adsorption capacity of Fe3O4@TpPa-1 still retained at a high level. According to Materials Studio simulation and XPS analysis, the adsorption mechanism was attributed to the presence of the homogeneously distributed imine and carbonyl functional groups in the framework of TpPa-1, allowing them to serve as platforms for anchoring heavy metals and organic pollutants. Besides, the hydrophobic skeleton structures of TpPa-1 endowed them good adsorption performance towards organic pollutants via hydrogen -bonding (NH…O…HO) and π-π interaction. Therefore, the recyclable Fe3O4@TpPa-1 showed a broad application prospects in environmental remediation.

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A covalent organic framework (COF) named TpPa-1 was designed and synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). It was utilized as a stationary phase in open-tubular capillary electrochromatography (OT-CEC). The column was coated with TpPa-1 using a covalent bonding strategy. The coated capillary was characterized by morphology, crystallography, and mesoporous analysis to confirm the successful fabrication. The OT-CEC method was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution (Rs > 1.81) and good precision (RSD < 4.9%). It takes about 12 h from COF preparation to OT-CEC separation. Graphical abstract A covalent organic framework (COF) named TpPa-1 was synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). COF-TpPa-1 modified capillary column was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution and good precision.

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Because of unique properties like permanent porosity, low density and large surface area, covalent organic frameworks are attractive microporous materials as stationary phase for CEC. Among them, COF-TpPa-1 possesses extraordinary chemical stability and common features of covalent organic frameworks. So, COF-TpPa-1 could be a promising material as stationary phase to enhance separation selectivity and tolerate the acid or alkaline electrochromatographic separation conditions. Here, we report the preparation of COF-TpPa-1 modified capillary column by in situ growth for electrochromatographic separation. The immobilization of COF-TpPa-1 on the inner wall of capillary column was confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray diffraction. The fabricated COF-TpPa-1 modified capillary column indicated good resolution for the separation of neutral analytes, nonsteroidal anti-inflammatory drugs and food additives in open-tubular CEC mode. Compared with bare capillary column, the COF-TpPa-1 modified capillary column improved separation selectivity remarkably for tested analytes, including hydrophobic, π-π and hydrogen bond interactions. Besides, the prepared capillary column showed excellent repeatability and stability. The intraday, interday and column-to-column relative standard deviations of migration time for neutral analytes were less than 3.54%. This work shows enamine-linked covalent organic frameworks have great potential as stationary phases in CEC.

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