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Accurate discrimination of metal species is a significant analytical challenge. Herein, we propose a novel methodology based on liquid-phase cyclic chemiluminescence (CCL) for the identification of cobalt speciation. The CCL multistage signals (In) of the luminol-H2O2 reaction catalyzed by different cobalt species have different decay coefficients k. Thereby, we can facilely identify various cobalt species according to the distinguishable k values, including the complicated and structurally similar cobalt complexes, such as analogues of [Co(NH3)5X]n+ (X = Cl-, H2O, and NH3), Co(II) porphyrins, and bis(2,4-pentanedione) cobalt(II) derivatives. Especially, the number of substituent atoms also influences the k value greatly, which allows excellent discrimination between complexes that only have a subtle difference in the substituent group. In addition, linear discriminant analysis based on In provides a complementary solution to improve the differentiating ability. We performed density functional theory calculations to investigate the interaction mode of H2O2 over cobalt species. A close negative correlation between the adsorption energy and the k value is observed. Moreover, the calculation of energy evolutions of H2O2 decomposition into a double hydroxide radical shows that a high level of consistency exists between the activation energy barrier and the k value. The results further demonstrate that the decay coefficient of the CCL multistage signal is associated with the catalytic reactivity of the cobalt species. Our work not only broadens the application of chemiluminescence but also provides a complementary technology for speciation analysis.
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Solid-phase microextraction (SPME) coupled with electrospray ionization mass spectrometry (ESI-MS) was developed for rapid and sensitive determination of endogenous androgens. The SPME probe is coated with covalent organic frameworks (COFs) synthesized by reacting 1,3,5-tri(4-aminophenyl)benzene (TPB) with 2,5-dioctyloxybenzaldehyde (C8PDA). This COFs-SPME probe offers several advantages, including enhanced extraction efficiency and stability. The analytical method exhibited wide linearity (0.1-100.0 µg L-1), low limits of detection (0.03-0.07 µg L-1), high enrichment factors (37-154), and satisfactory relative standard deviations (RSDs) for both within one probe (4.0-14.8%) and between different probes (3.4-12.7%). These remarkable performance characteristics highlight the reliability and precision of the COFs-SPME-ESI-MS method. The developed method was successfully applied to detect five kinds of endogenous androgens in female serum samples, indicating that the developed analytical method has great potential for application in preliminary clinical diagnosis.
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Androgênios , Limite de Detecção , Microextração em Fase Sólida , Espectrometria de Massas por Ionização por Electrospray , Microextração em Fase Sólida/métodos , Espectrometria de Massas por Ionização por Electrospray/métodos , Humanos , Androgênios/sangue , Androgênios/análise , Androgênios/química , Feminino , Estruturas Metalorgânicas/química , Reprodutibilidade dos TestesRESUMO
The similarity and complexity of chiral amino acids (AAs) in complex samples remain a significant challenge in their analysis. In this work, the chiral metal-organic framework (MOF)-controlled cyclic chemiluminescence (CCL) reaction is developed and utilized in the analysis of enantiomer AAs. The chiral MOF of d-Co0.75Zn0.25-MOF-74 is designed and prepared by modifying the Co0.75Zn0.25-MOF-74 with d-tartaric acid. The developed chiral bimetallic MOF can not only offer the chiral recognize sites but also act as the catalyst in the cyclic luminol-H2O2 reaction. Moreover, a distinguishable CCL signal can be obtained on enantiomer AAs via the luminol-H2O2 reaction with the control of d-Co0.75Zn0.25-MOF-74. The amplified difference of enantiomer AAs can be quantified by the decay coefficient (k-values) which are calculated from the exponential decay fitting of their obtained CCL signals. According to simulation results, the selective recognition of 19 pairs of AAs is controlled by the pore size of the MOF-74 and their hydrogen-bond interaction with d-tartaric acid on the chiral MOF. Furthermore, the k-values can also be used to estimate the change of chiral AAs in complex samples. Consequently, this chiral MOF-controlled CCL reaction is applied to differentiate enantiomer AAs involved in the quality monitoring of dairy products and auxiliary diagnosis, which provides a new approach for chiral studies and their potential applications.
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Aminoácidos , Estruturas Metalorgânicas , Aminoácidos/análise , Luminescência , Luminol/química , Peróxido de Hidrogênio/química , Estruturas Metalorgânicas/químicaRESUMO
Here, an imine-linked-based spherical covalent organic framework (COF) was prepared at room temperature. The as-synthesized spherical COF served as an adsorbent in dispersive solid-phase extraction (dSPE), by its virtue of great surface area (1542.68 m2 /g), regular distribution of pore size (2.95 nm), and excellent stability. Therefore, a simple and high-efficiency dispersive solid phase extraction method based on a spherical COF coupled with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established to determine aryl organophosphate esters in biological samples. This approach displayed favorable linearity in the range of 10.0-1000.0 ng/L (r > 0.9989), a high signal enhancement factor (58.8-181.8 folds) with low limits of detection (0.3-3.3 ng/L). Moreover, it could effectively eliminate complex matrix interference to accurately extract seven aryl organophosphate esters from mouse serum and tissue samples with spiked recoveries of 82.0%-117.4%. The as-synthesized spherical COF has been successfully applied in sample preparation. The dSPE-HPLC-MS/MS method based on a spherical COF has potential application to study the pollutants' metabolism in vivo.
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Estruturas Metalorgânicas , Espectrometria de Massas em Tandem , Animais , Camundongos , Espectrometria de Massas em Tandem/métodos , Estruturas Metalorgânicas/química , Cromatografia Líquida de Alta Pressão , Extração em Fase Sólida/métodos , Adsorção , Limite de DetecçãoRESUMO
A cataluminescence (CTL) method has been developed for the rapid determination of acetic acid in enzyme products. The NiMn LDH/CNT/GO was synthesized based on the nanohybridization of NiMn layered double hydroxide (NiMn LDH), carbon nanotubes (CNTs), and graphene oxide (GO). The composite has excellent CTL activity against acetic acid. It could be ascribed to the larger specific surface area and more exposure to active sites. NiMn LDH/CNT/GO is used as a catalyst in the CTL method based on its special structure and advantages. There is a linear relationship between CTL response and the acetic acid concentration in the range 0.31-12.00 mg·L-1 with the detection limit of 0.10 mg·L-1. The developed method is rapid and takes only about 13 s. The method is applied to the determination of acetic acid in enzyme samples with little sample preparation. The result of the CTL method shows good agreement with that of the gas chromatography method. The proposed CTL method possesses promising potential in the quality monitoring of enzymes.
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Nanotubos de Carbono , Nanotubos de Carbono/química , Ácido Acético , Hidróxidos/químicaRESUMO
The integration of metallic oxide and metal-organic frameworks has attracted considerable attention as obtained composite materials because they show synergistic effects in applications of catalysis and sensing. Herein, we developed the hybrid MgO and HKUST-1 for efficient capture, catalysis, and cyclic cataluminescence (CCTL) detection of esters all-in-one to rapidly identify scented products. The multifunctional MgO/HKUST-1 composite with high CCTL activity was synthesized and characterized. The multifunctional MgO/HKUST-1 composite acts as an enrichment material for ester capture and serves as a catalyst, assisting the analyte to trigger multistage signals. The multistage signals of ester-containing scented products also satisfy the exponential decay equation with a certain τ-value. The τ-values obtained by the CCTL system were applied to identify the brands of essential oils. The working temperature served as the sensor element to obtain various τ-values. The τ-values constituted a digital code to label the different brands of cigarettes with the same aroma type. The multistage signals could be used to distinguish the origin regions of essential oils and tobacco. This work combines the CCTL strategy with the sample pretreatment, opening up a new direction to develop CCL and providing a new platform to rapidly identify ester-containing scented products.
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Estruturas Metalorgânicas , Catálise , Ésteres , Óxido de MagnésioRESUMO
Oesophageal bezoars are one of the many causes of nasogastric tube obstruction; however, they are extremely rare and, therefore, not often considered to be the cause of a blockage. A bezoar is a solid mass of indigestible material that accumulates in the digestive tract. After a blockage is identified, the nasogastric tube is usually removed and another one inserted. However, this can be dangerous and can easily cause tearing of the oesophageal mucosa, bleeding, and other serious complications. In this article, the authors present a case of nasogastric tube obstruction caused by oesophageal bezoars. After the nasogastric tube was replaced, the patient experienced two tears of the oesophageal mucosa. This article highlights the importance of the introduction of a procedure for nurses to follow in cases of nasogastric tube obstruction, bearing in mind the possibility of the presence of oesophageal bezoars. If necessary, a gastroscope should be used to ensure safe insertion of the nasogastric tube and prevent oesophageal mucosal tears.
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Bezoares , Mucosa Esofágica , Esôfago/diagnóstico por imagem , Humanos , Intubação Gastrointestinal/efeitos adversosRESUMO
Identification of complex samples presents a difficult challenge for modern analytical techniques, and the differentiation among closely similar mixtures often remains indeterminate. In this article, we designed a simplified cyclic chemiluminescence (CCL) system that is able to measure multistage signals in a single sample injection. The system was used to investigate the CCL reactions of the binary, ternary, and multicomponent mixtures. Results showed that each mixture has a unique exponential decay equation (EDE) with a constant decay coefficient (k-value) to describe the change law of its multistage signals. Further studies found that different brands of liquor, beer, toner, and baby powder have different k-values, and the same brand of the commodities between different batches have the same k-values, which allows facile identification of these complex samples. We then used different catalysts to design digital codes of the k-value for further improving the identifying ability of CCL. Moreover, the multistage signals are like fingerprints and could be used for linear discriminate analysis, which provides another complementary approach for identification of complex samples. Finally, we demonstrated that CCL shows potential applications in certification and quality assurance according to the change of the k-values of the sample. This work demonstrates that excellent discrimination ability of CCL for the identification of complex samples and provides a promising technology for quality assurance.
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The authors describe a strategy for ozone-induction coupling with plasma assistance (O3-I/PA) to enhance cataluminescence (CTL) based sensing of volatile organic compounds (VOCs). A homemade O3-I/PA CTL sensor system was constructed based on this strategy. O3-I/PA can significantly enhance the CTL response to many compounds that were hardly detectable previously with adequate sensitivity. Without any preconcentration, the limits of detection (for S/N = 3) are 20 µg.m-3 (= 5 ppbv) for toluene and 8 µg.m-3 (6.4 ppbv) for formaldehyde. VOCs including benzene, alkanes, halohydrocarbons, alkenes alcohols, aldehydes, ketones and ethers are found to produce a strong response when using this sensor system. Mechanistic studies showed that the synergistic effect of ozone-induction and plasma assistance promote the oxidation of the VOCs under formation of CO2. This strongly favors CTL emission. The sensor system can be used as a direct-reading detector for on-line and real-time monitoring of total VOCs. It also can be used as a detector in gas chromatography for the identification of individual VOCs. It is perceived that this work paves the way to both a new kind of vapor sensor and to a detection scheme in gas chromatography. Graphical abstract The synergistic effect of ozone-induction and plasma assistance promote the deep oxidation of the VOCs into CO2, which strongly favors cataluminescence emission.
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Different formulations of foaming polyurethane grout offer controlled expansion rates. This is crucial for precision in filling voids without exerting excessive pressure on surrounding structures, which could potentially cause damage. This study focuses on the impact of composition on the expansion performance of tailor-made polyurethane grouting materials. Initially, multiple unknown chemical reaction kinetic parameters were identified by combining free expansion tests, which involved measuring density and temperature changes, with the particle swarm optimization algorithm. A numerical simulation, integrating chemical kinetic models and fluid flow equations, was established to replicate the free expansion process of polyurethane grout in a cup, aligning with our experimental results. Subsequently, we analyzed the polymerization process of polyurethane grout with varying compositions to determine the effect of composition ratios on grout expansion. Our findings reveal that the expansion ratio of foaming polyurethane is predominantly influenced by the concentrations of physical and chemical foaming agents, followed by isocyanate concentration. Polyol, in contrast, exerts a relatively minor influence. Furthermore, the solubility of the physical foaming agent in the grout determines both its maximum allowable concentration and its maximum contribution to volume increase. This study provides valuable insights for the design and selection of polyurethane grout components tailored to diverse applications.
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Triclosan (TCS), triclocarban (TCC), and chlorophenols (CPs) are broad-spectrum antibacterials widely used in dermatological and oral hygiene products, which could induce severe liver and intestine injuries. Hence, it is essential to establish a rapid and sensitive method to monitor TCS, TCC, and CPs in various organisms. In this work, fluorine-functionalized covalent organic framework (COF-F) was prepared by using 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tri-aniline and 2,3,5,6-tetrafluoroterephthalaldehyde as two building units and employed as a solid phase microextraction (SPME) probe for the extraction of TCS, TCC and CPs. The COF-F possessed excellent hydrophobicity, a large specific surface area (1354.3 m2 g-1) and high uniform porosity (3.2 nm), which facilitated high selectivity and adsorption properties towards TCS, TCC, and CPs. Therefore, the as-prepared COF-F-SPME in combination with electrospray ionization mass spectrometry has been developed to provide fast and ultrasensitive detection of TCS, TCC, and CPs in biological samples. The established method demonstrated satisfactory linear ranges (0.01-100.00 µg L-1) and low limits of detection (0.003-0.040 µg L-1) for TCS, TCC and CPs. The developed method could be successfully applied to detect TCS, TCC and CPs in the liver and kidney tissues of mice, demonstrating the potential for the detection of chlorinated aromatic pollutants in the biological samples.
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Carbanilidas , Clorofenóis , Microextração em Fase Sólida , Espectrometria de Massas por Ionização por Electrospray , Triclosan , Animais , Microextração em Fase Sólida/métodos , Triclosan/análise , Triclosan/química , Carbanilidas/análise , Camundongos , Clorofenóis/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Flúor/química , Estruturas Metalorgânicas/química , Limite de Detecção , MasculinoRESUMO
Significant impairment of pulmonary function has been demonstrated through long-term exposure to neonicotinoid insecticides, such as imidacloprid (IMI). However, the underlying mechanisms of lung injury induced by IMI remain unclear. In this study, a mouse model of IMI-induced pulmonary injury was established, and the toxicity and lung damage were assessed through mouse body weight, organ index, hematological parameters, and histopathological analysis of lung tissues. Furthermore, metabolomics and transcriptomics techniques were employed to explore the mechanistic aspects. Results from the toxicity assessments indicated that mouse body weight was significantly reduced by IMI, organ index was disturbed, and hematological parameters were disrupted, resulting in pulmonary injury. The mechanistic experimental results indicate that the differences in metabolites and gene expression in mouse lungs could be altered by IMI. Validation of the results through combined analysis of metabolomics and transcriptomics revealed that the mechanism by which IMI induces lung injury in mice might be associated with the activation of the TLR4 receptor, thereby activating the PI3K/AKT/NF-κB signaling pathway to induce inflammation in mouse lungs. This study provided valuable insights into the mechanisms underlying IMI-induced pulmonary damage, potentially contributing to the development of safer pest control strategies. The knowledge gained served as a robust scientific foundation for the prevention and treatment of IMI-related pulmonary injuries.
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Inseticidas , Lesão Pulmonar , NF-kappa B , Neonicotinoides , Nitrocompostos , Fosfatidilinositol 3-Quinases , Proteínas Proto-Oncogênicas c-akt , Transdução de Sinais , Receptor 4 Toll-Like , Animais , Neonicotinoides/toxicidade , Nitrocompostos/toxicidade , Camundongos , Lesão Pulmonar/induzido quimicamente , Transdução de Sinais/efeitos dos fármacos , Fosfatidilinositol 3-Quinases/metabolismo , NF-kappa B/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , Inseticidas/toxicidade , Receptor 4 Toll-Like/metabolismo , Pulmão/efeitos dos fármacos , Pulmão/patologiaRESUMO
Inorganic elements in the environment and organisms play a vital role in environmental safety assessment and metallomics study. The environment-related samples, including water, soil, air, food, energy oil, mineral, and waste are generally complex matrices due to the existence of organic and inorganic matter. Sample preparation is often fundamental prior to instrumental analysis. Therefore, sample preparation methods with selectivity, sensitivity, high speed, and automation are desired. This review summarized 3 kinds of environmental sample preparation, including phase separation strategy, field-assisted acceleration strategy, and integration system strategy for total elemental analysis and speciation analysis. Emphasis will be raised on the presentation of the most exemplified works published in 2017-2022.
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Óleo Mineral , Solo , ÁguaRESUMO
In this work, a catalytic material of cobalt doped nitrogenous porous carbon (Co/NPC) was fabricated from covalent organic frameworks (COFs) and cobalt ion via directly carbonization. Attribute to the excellent selective catalytic performance towards n-hexane, Co/NPC was employed in cataluminescence (CTL) for rapid and sensitive determination of n-hexane. Moreover, the detection conditions of CTL were evaluated, including temperature, flow rate and detecting wavelength. Under optimized conditions, a good linear relation between signal intensity of CTL and n-hexane concentration was obtained in the linear range of 0.4-250.0 mg/L and the limit of detection (LOD, S/N = 3) was 0.13 mg/L. Furthermore, the Co/NPC based CTL sensor was successfully applied to the determination of n-hexane in edible oil samples with the recoveries in the range of 92.0%-104.0%. The method comparison results of GC/MS and CTL on real sample analysis further proved the accuracy of the developed Co/NPC based CTL method. Additionally, the possible catalytic mechanism of n-hexane on the surface of Co/NPC was investigated, assisting by GC/MS on intermediation products identification. Overall, the Co/NPC based CTL sensor has been confirmed excellent performance in the n-hexane determination, which revealing extensive application in rapid residual n-hexane analysis in edible oil.
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Rapid chiral analysis has become one of the important aspects of academic and industrial research. Here we describe a new strategy based on liquid-phase cyclic chemiluminescence (CCL) for rapid resolution of enantiomers and determination of enantiomeric excess (ee). A single CCL measurement can acquire multistage signals that provide a unique way to examine the intermolecular interactions between chiral hosts and chiral guests, because the lifetime (τ) of the multistage signals is a concentration-independent and distinguishable constant for a given chiral host-guest system. According to the τ values, CCL allows discrimination between a wide range of enantiomeric pairs including chiral alcohols, amines and acids by using only one chiral host. Even the chiral systems hardly distinguished by nuclear magnetic resonance and fluorescence methods can be distinguished easily by CCL. Additionally, the τ value of a mixture of two enantiomers is equal to the weighted average of each enantiomer, which can be used for the direct determination of ee without the need to separate the chiral mixture and create calibration curves. This is extremely crucial for the cases without readily available enantiomerically pure samples. This strategy was successfully applied to monitoring of the Walden inversion reaction and analysis of chiral drugs. The results were in good agreement with those obtained by high-performance liquid chromatography, indicating the utility of CCL for routine quick ee analysis. Mechanism study revealed that the τ value is possibly related to the activity of the chiral substance to catalyze a luminol-H2O2 reaction. Our research provides an unprecedented and general protocol for chirality differentiation and ee determination, which is anticipated to be a useful technology that will find wide application in chirality-related fields, particularly in asymmetric synthesis and the pharmaceutical industry.
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Isomers discrimination plays a vital role in modern chemistry, and development of efficient and rapid method to achieve this aim has attracted a great deal of interest. In this work, a novel carbon dot-decorated chiral porous organic cage hybrid nanocomposite (CD@RCC3) was prepared and used to fabricate fluorescent sensor. The resultant CD@RCC3 was characterized by using a range of techniques, finding that CD@RCC3 possesses strong and stable fluorescent property in common organic solvents, especially it exhibits chiral property. The potential application of CD@RCC3 in fluorescence sensing was demonstrated by isomers discrimination. The designed sensor was successfully used to rapid discriminate nitrophenol isomers. Meanwhile, it exhibited differentiation ability towards phenylalaninol and phenylethanol enantiomers. Our work enriches the type of synthetic materials for fluorescence sensing, and provides a simple method for distinguishing structural isomers and chiral isomers.