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ELECTROPHORESIS · 2018 ·Vol. 39 ·期 22 ·2912-2918 · IF 2.569

Covalent organic framework TpPa-1 as stationary phase for capillary electrochromatographic separation of drugs and food additives

Deying Kong,Zilin Chen

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.

研究领域: 分析化学 · 材料科学
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2022 · IF 10.319

Construction of highly active WO3/TpPa-1-COF S-scheme heterojunction toward photocatalytic H2 generation

Long Sun,Lingling Li,Jiajie Fan,Quanlong Xu,Dekun Ma

The rapid charge recombination and low surface reaction kinetics are the two major constraints to the photocatalytic performance of covalent organic frameworks (COFs). To accelerate the charge separation behavior, TpPa-1-COF is decorated with WO 3 via an in-situ growth approach, and the resultant WO 3 /TpPa-1-COF composites show significantly improved photocatalytic performance. Especially, when the WO 3 loading arrives at 3 wt%, 3%WO 3 /TpPa-1-COF exhibits the maximum photocatalytic H 2 evolution rate of 19.89 mmol g −1 h −1 , which is approximately 4.8 times higher than that of pure TpPa-1-COF. The apparent quantum efficiency (AQE) of 3%WO 3 /TpPa-1-COF at 420 nm is detected to be 12.4%. X-ray photoelectron spectroscopy (XPS) characterization confirms the formation of internal electric field between WO 3 and TpPa-1-CF, which can drive the photogenerated charge carrier diffusion in S-scheme mode. As a result, WO 3 /TpPa-1-COF composite possesses high charge separation efficiency and strong redox ability, which is further supported by the photoelectrochemical results, thus benefiting the photocatalysis process. This work provides a rational strategy to modify COFs in photocatalytic water splitting.

CAS / MDL: 106-50-3 10213-10-2
研究领域: 材料科学 · 光催化
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ANALYTICA CHIMICA ACTA · 2020 · IF 5.977

In-situ layer-by-layer synthesized TpPa-1 COF solid-phase microextraction fiber for detecting sex hormones in serum

Jiating Zheng,Shuyao Huang,Yuanjun Tong,Songbo Wei,Guosheng Chen,Siming Huang,Gangfeng Ouyang

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 μ m 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.

研究领域: 分析化学 · 医学检测 · 材料科学
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Foods · 2022 ·Vol. 11 ·期 19 ·3130 · IF 5.561

Development of a Sensitive and Fast Determination Method for Trace Carbaryl Residues in Food Samples Based on Magnetic COF (TpPa-NH2)@Fe3O4 Nanoparticles and Fluorescence Detection

Juanli Du,Hao Wu,Xu Jing,Yonghe Yu,Zhisheng Yan,Jianhai Zhang

Developing a simple and effective method for measuring carbaryl residues in food is urgent due to its widespread use and the associated health risks in agriculture, as well as various defects in existing detection techniques. The COF (TpPa-NH2)@Fe3O4nanocomposite (amino modification) was synthesized via a two-step method and used as an adsorbent for the extraction of carbaryl from food samples in this study. The results indicated that COF (TpPa-NH2)@Fe3O4can rapidly and successfully capture carbaryl directly from samples via π–π stacking and hydrophobic interactions, achieving maximum adsorption within 5 min under a small adsorbent quantity using a fluorescence spectrophotometer. Under the optimized conditions, carbaryl exhibited good linearity in the range of 0.2–120 µg·kg−1, and the limit of detection was 0.012 µg·kg−1. The recoveries of the samples were 96.0–107.4%. This method has broad application prospects for the monitoring of carbaryl in food.Keywords:magnetic solid-phase extraction;COF (TpPa-NH2)@Fe3O4nanocomposite;fluorescence spectroscopy;carbaryl;food samples

研究领域: 食品安全 · 分析化学
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FOOD CHEMISTRY · 2023 · IF 8.8

A molecularly imprinted photopolymer based on mesh TpPa-2 embedded with perovskite CsPbBr3 quantum dots for the sensitive solid fluorescence sensing of patulin in apple products

Qiuxue Leng,Shuang Han,Minghui Zhai,Shiwei Liu,Yuzhuo Song

Here, a novel molecularly imprinted photopolymer was prepared using CsPbBr 3 quantum dots as the fluorescence source, TpPa-2 as substrate for selective solid fluorescence detection of patulin (PAT). TpPa-2 can promote efficient recognition of PAT due to its unique structure and significantly improve the fluorescence stability and sensitivity. The test results showed that the photopolymer exhibited large adsorption capacity (131.75 mg/g), fast adsorption ability (12 mins), superior reusability and high selectivity. The sensor proposed had good linearity for PAT in the range of 0.2–20 ng/mL and was applied to the analysis of PAT in apple juice and apple jam with a limit of detection as low as 0.027 ng/mL. Therefore it maybe a promising method for solid fluorescence detection of trace PAT in food analysis.

研究领域: 材料科学 · 分析化学 · 食品科学
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FOOD CHEMISTRY · 2022 · IF 9.231

Preparation of mesh covalent organic framework Tppa-2-based adsorption enhanced magnetic molecularly imprinted composite for selective extraction of tetracycline residues from animal-derived foods

Shuang Han,Qiuxue Leng,Fu Teng,Yuxin Ding,Aixin Yao

In this study, for the first time, core–shell tetracycline hydrochloride-molecularly imprinted polymers (MIPs) were prepared by precipitation polymerization using a magnetic covalent organic framework (Fe 3 O 4 @Tppa-2) synthesized by room-temperature ultrasonic method as a substrate. Introducing Fe 3 O 4 @Tppa-2 into the molecular imprinting system can be used for efficient shortens the time for the adsorption equilibrium of MIPs due to its unique pore structure. The maximum adsorption capacity of MIPs was 87.50 mg/g, and the adsorption equilibrium reached in 14 min. The MIPs were used as magnetic solid-phase extraction sorbents in combination with high performance liquid chromatography for the determination of tetracycline in pork, chicken and chicken liver, and the detection limit reached 0.01 ng/mL. In addition, the adsorption advantages of MIPs suggest that it is a promising adsorbent for the recovery of antibiotics and has potential applications in the detection and enrichment of TC in food.

研究领域: 材料科学 · 分析化学 · 食品科学
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ACS Applied Polymer Materials · 2025 · IF 4.7

Alkali Metal-Functionalized Covalent Organic Frameworks for CO2 Adsorption and CO2/N2 Separation

Jinpeng Liu,Chengcheng Hao,Huili Zhang,Hongyu Chen,Ling Zhang,Xiaodong Chen,Jianye Wang,Maohuai Wang,Shuxian Wei,Xiaoqing Lu,Zhaojie Wang,Siyuan Liu

Covalent organic frameworks (COFs) have become potential candidates for gas purification technology, especially in carbon capture and storage applications. By utilizing strategies such as pore structure design and functional modification, COFs have been developed to exhibit high selectivity and superior adsorption capacity for the effective capture and separation of CO2 from industrial waste gases. Notably, alkali metals exhibit strong interactions with the backbone of the COFs, which can enhance the CO2/N2 adsorption separation performance of these porous materials. This study details the synthesis of two-dimensional COF materials modified with acidic groups (TpPa-COOH and TpPa-SO3H) via mechanical grinding. Alkali metals such as Na, Li, and K were introduced into these groups through simple ion exchange reactions, thereby creating metal-modified COF materials. The impact of various alkali metals on the CO2/N2 adsorption separation performance of COF materials was investigated. Among the resulting products, lithiated TpPa-COOH showed the highest CO2 capture capacity of 2.65 mmol/g at 273 K and 1 bar. This may be due to the smaller atomic size of Li that offers larger adsorption space. Under the same conditions, the K-modified TpPa-SO3H exhibited the highest selectivity of 548, which surpasses most COFs reported in the literature. The superior performance was caused by the high polarization of the COF backbone triggered by the alkali metals. The inference was further confirmed by computational simulations. This work provides a facile method for the modification of porous materials with alkali metals to achieve superior gas separation performance.

CAS / MDL: 546-89-4
研究领域: 材料科学 · 环境科学
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APPLIED SURFACE SCIENCE · 2019 · IF 5.155

Highly efficient enrichment mechanism of U(VI) and Eu(III) by covalent organic frameworks with intramolecular hydrogen-bonding from solutions

Xin Zhong,Wen Liang,Zhipeng Lu,Baowei Hu

In this investigation, TpPa-1 were synthesized and exploited for radionuclides ions elimination. According to Langmuir model, at pH 6.5 and 298 K, the maximum adsorption quantity of TpPa-1 were 1194.07 mg(U(VI))/g and 1107.63 mg(Eu(III))/g, respectively. The superior adsorption performance could be attributed to: (i) a great quantity of heteroatom activated sites on the pore wall could conduct as cation receptors; (ii) the forming intramolecular C N … H … O hydrogen bonding in the network of TpPa-1, which was U(VI) and Eu(III) ions adsorption sites; (iii) hydrogen bonding could adjust the electron density of the complex and abate the total charge of radionuclides. The outcomes of this work suggest that TpPa-1 is a promising adsorbent, which is appropriate to enrichment and separation radionuclides from polluted wastewater.

研究领域: 环境科学 · 材料科学
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Animals · 2026 ·Vol. 16 ·期 15 ·2282 · IF 3.2

Toxicity of the Covalent Organic Framework Material TpPa to Zebrafish

Cuiming Huang,Jingui Lin,Xiudan Yang,Lu Gan,Lijie Xu,Muting Yan,Han Gong

Simple SummaryCovalent organic frameworks (COFs) are promising materials for environmental cleanup due to their unique structures. However, little is known about their safety for aquatic life once they are released into water. This study used zebrafish (Danio rerio), a small freshwater fish commonly used in toxicity testing, to evaluate the harmful effects of a typical COF material called TpPa (Tp = 1,3,5-triformylphloroglucinol, Pa =p-phenylenediamine). Zebrafish embryos and larvae were exposed to different concentrations of TpPa for 120 h. The results showed that TpPa caused damage in a dose-dependent manner, with obvious developmental effects observed, including delayed hatching, physical deformities, reduced growth, abnormal heart rates, and altered swimming behavior. Further investigation revealed that TpPa induced oxidative stress and activated cell death pathways, ultimately disrupting normal development through a cascade mechanism. These findings provide important information for setting safety limits and assessing the ecological risks of TpPa and similar COF materials in aquatic environments.Covalent organic frameworks (COFs) show great potential in environmental remediation, yet the aquatic safety of TpPa (Tp = 1,3,5-triformylphloroglucinol, Pa =p-phenylenediamine), a typical COF, remains unclear. This study employed zebrafish (Danio rerio) to evaluate the environmental toxicity of TpPa and elucidate molecular mechanisms. Zebrafish embryos were exposed to 0–50 mg/L TpPa for 120 h, and developmental toxicity, oxidative stress, and physiological and molecular responses were investigated. Results demonstrated that TpPa exposure exerted concentration- and time-dependent effects. Mortality and malformation rates increased significantly from 5 mg/L, accompanied by reduced body length. The hatching rate showed a biphasic pattern, increasing with concentration at 48 h and decreasing with concentration at 120 h. Spontaneous movement was elevated at 50 mg/L, while heart rate increased dose-dependently starting from 5 mg/L at 48 h and from 1 mg/L at 72 h. Mechanistically, TpPa induced oxidative stress via reactive oxygen species accumulation and impaired the activities of both superoxide dismutase and catalase. These effects activated thep53-mediated apoptotic pathway, reduced theBcl2/Baxratio, and disrupted theGH/IGFgrowth axis and neuromotor regulatory pathways, ultimately causing developmental abnormalities. These findings provide critical data for the environmental safety assessment of TpPa, with direct relevance to establishing health monitoring protocols for COF-exposed aquaculture species.

CAS / MDL: 80-41-1
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ANALYST · 2017 ·Vol. 142 ·期 17 ·3212-3218 · IF 3.885

Highly efficient enrichment of N-linked glycopeptides using a hydrophilic covalent-organic framework

Yu-Fang Ma,Fang Yuan,Xiao-Hui Zhang,Ying-Lin Zhou,Xin-Xiang Zhang

The enrichment of glycopeptides plays an important role in glycoproteomics. In this paper, a covalent-organic framework called TpPa-1, synthesized by the Schiff base reaction of 1,3,5-triformylphloroglucinol and paraphenylenediamine, was first successfully utilized as a hydrophilic porous material for N-linked glycopeptide enrichment. Using this material, interference from non-glycopeptides could be efficiently eliminated, which facilitated the mass spectrometry detection of glycopeptides. By capturing N-linked glycopeptides from tryptic digests of human IgG, our method was proved to have high sensitivity at the femtomole level. And it showed superior selectivity for glycopeptides even when non-glycopeptides were 1000 times more concentrated. Due to the strong covalent bonds, this material possessed good stability and could be repeatedly used for at least 10 times. The ultra-low mass density and abundant binding sites also provided it with high binding capacity (178 mg g−1, IgG/TpPa-1). Moreover, N-linked glycopeptides were easily enriched by this material from only 10 μL human serum, which demonstrated its potential in pretreatment of complex biological samples.

CAS / MDL: 76-05-1
研究领域: 蛋白质组学 · 分析化学 · 生物医学
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CERAMICS INTERNATIONAL · 2023 · IF 5.2

Photothermocatalytic sterilization activity enhancement and mechanism evaluation of WO3/TpPa-1/N-Nb2CTx constructed with a 2D Z-type heterojunction WO3/TpPa-1 and 2D co-catalyst Nb2CTx

Yirui Zhao,Hongshun Hao,Jiaqi Zhong,Gongliang Zhang,Jingran Bi,Shuang Yan,Feng Hong,Hongman Hou

Foodborne pathogens are the main factors causing food poisoning, and it is of great significance to develop novel nanocomposites to obtain efficient and stable photothermal-assisted photocatalysts for killing foodborne pathogens. In this paper, Z-type heterojunction WO 3 /TpPa-1 with a core-shell structure was constructed by in-situ synthesis, and the Nb 2 CT x was used as a co-catalyst to obtain an efficient ternary composite WO 3 /TpPa-1/N-Nb 2 CT x . Compared to the monomers, the ternary composites improved light trapping, interfacial separation effectiveness, and the mobility of photogenerated carriers. The WO 3 /TpPa-1/15% N-Nb 2 CT x has the best sterilization efficiency of 99.69% under visible-infrared light irradiation for 30 min. The construction of WO 3 /TpPa-1/N-Nb 2 CT x promoted the separation of electron and hole pairs, which improved the electron transport efficiency and the generation of reactive oxygen species. In addition, the excellent photothermal effect of Nb 2 CT x improves the sterilization performance of WO 3 /TpPa-1/N-Nb 2 CT x . The WO 3 /TpPa-1/N-Nb 2 CT x has a broad application prospect in photothermal-assisted photocatalytic sterilization.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Enhanced selective electrosorption of Pb2+ from complex water on covalent organic framework-reduced graphene oxide nanocomposite

Hao Zhang,Xiaodie Li,Chengming Xiao,Jia Xie,Xin Yan,Chaohai Wang,Yujun Zhou,Junwen Qi,Zhigao Zhu,Xiuyun Sun,Jiansheng Li

Selective capture of the toxic and ubiquitous heavy metal ions is crucially desired yet still significant challenge for water purification. Herein, a covalent organic framework-reduced graphene oxide nanocomposite (TpPa@rGO) was developed and employed as cathode for the first time to selectively remove Pb 2+ from complex water via an electrosorption process. Specifically, the rGO provides the electrical conductivity and induces the electric double layer capacitance to attract cations approaching to the electrode surface, while the TpPa endows abundant highly selective redox-active sites to capture Pb 2+ . Thanks to the ingenious synergy of capacitive rGO and redox-active TpPa, more than 99.6% of Pb 2+ can be effectively removed by the TpPa@rGO electrode in a mixed solution containing Pb(NO 3 ) 2 (50 mg L −1 ) and multicomponent nitrates (100 mg L −1 for each), as well as good cycling stability. Interestingly, the interfering ions can serve as additional electrolytes to accelerate the accumulation of Pb 2+ around the TpPa@rGO electrode instead of competing for active sites, thereby increasing the absolute adsorption capacity of Pb 2+ from 94.6 mg g −1 in single Pb(NO 3 ) 2 solution to 129.8 mg g −1 in the multicomponent solution. The enhanced selective electrosorption mechanism on Pb 2+ removal by TpPa@rGO and their recyclability were also investigated. The capacitive matrix and additional electrolytes accelerate the ion transfer and enhance ion accessibility to the electrode, thereby anchoring the Pb 2+ on the N/O groups of TpPa. This study may put forward a promising method for the selective capture of heavy metal ions in complex water.

研究领域: 环境科学 · 材料科学 · 化学工程 · 水处理
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