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Background: China started to implement the HPV vaccination program for females in 2016. This study investigated associations between mothers' decisional conflicts, satisfaction with governmental health promotion materials, and their daughters' HPV vaccination uptake. Methods: A cross-sectional online survey was conducted between July and October 2023 among mothers of girls aged 9-17 years in Shenzhen, China. Participants were mothers having a daughter aged 9-17 years at the survey date and a smartphone with internet access. About 3 % of all primary and secondary schools in Shenzhen were randomly selected by the research team (11 primary schools and 13 secondary schools). Teachers at the selected schools invited mothers of female students aged 9-17 years to complete an anonymous online questionnaire. Multivariate logistic regression was fitted. Results: Among 11,728 mothers who completed the survey, 18.9% of their index daughters received at least one dose of HPV vaccination. In multivariate analysis, less decisional conflict about the choice of HPV vaccines for their daughters (AOR: 1.07, 95%CI: 1.05, 1.10), more satisfaction with the government's health promotional materials related to HPV vaccines (AOR: 1.15, 95%CI: 1.12, 1.19), receiving more cue to action from significant others (AOR: 1.23, 95%CI: 1.19, 1.27), and perceived higher self-efficacy related to HPV vaccines (AOR: 1.79, 95%CI: 1.67, 1.92) were associated with a higher uptake of HPV vaccines. Perceived susceptibility to HPV (AOR: 0.79, 95%CI: 0.74, 0.85), perceived barriers to having the index daughter receive HPV vaccines (AOR: 0.82, 95%CI: 0.80, 0.84), and mothers who were hesitant to receive HPV vaccination (AOR: 0.75, 95%CI: 0.68, 0.84) were associated with a lower uptake. Conclusion: HPV vaccination uptake was low among girls in China. Future health promotion should address mothers' decisional conflicts about the choice of HPV vaccines for their daughters and improve the health promotional materials. School-based HPV vaccination programs might be useful.
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BACKGROUND: Mothers play a crucial role in influencing their daughters' HPV vaccination decisions. Addressing barriers to receiving HPV vaccination among mothers of girls may achieve two goals in one strike: increasing vaccination coverage among both mothers and their daughters. This study aims to examine the HPV vaccination uptake and its determinants among mothers of girls in China at both the individual and interpersonal levels. METHODS: From July to October 2023, a cross-sectional online study was conducted to investigate HPV vaccine refusal for daughters aged 9-17 years among 11,678 mothers in Shenzhen, China. A randomized selection method was employed, targeting 11 primary schools and 13 secondary schools in Shenzhen. The research team invited mothers of girls to participate in an anonymous online survey. Multilevel logistic regression models (level 1: schools; level 2: individual participants) were employed to analyze the data. RESULTS: Among 11,678 mothers, 41.1% self-reported receiving at least one dose of HPV vaccination. Through multilevel logistic regression analysis, eight items measuring illness representations of HPV, which refers to how people think about HPV, were associated with higher HPV vaccination uptake (AOR: 1.02-1.14). These items included identity (identifying symptoms of HPV), timeline (whether HPV is acute/chronic), negative consequences, personal and treatment control (whether HPV is under volitional control), concern, negative emotions, and coherence (overall understanding of HPV). In addition, participants refusing HPV vaccines for the index daughters (AOR: 0.82, 95%CI: 0.76, 0.89) had lower vaccine uptake. Perceived more difficulties in accessing the 9-valent vaccines (AOR: 1.06, 95%CI: 1.04, 1.08) and more satisfaction with vaccine-related promotional materials (AOR: 1.50, 95%CI: 1.46, 1.54) at the individual level were associated with higher vaccine uptake. At the interpersonal factors, higher frequency of exposure to testimonials given by others about HPV vaccination on social media (AOR: 1.19, 95%CI: 1.14, 1.25) and thoughtful consideration of the veracity of the information (AOR: 1.11, 95%CI: 1.07, 1.16) were correlated with higher HPV vaccination uptake. CONCLUSIONS: These findings offer essential implications for modifying HPV disease perceptions, addressing difficulties in accessing the 9-valent HPV vaccines, and enhancing health communication needs to improve HPV vaccine uptake among mothers of girls.
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Madres , Infecciones por Papillomavirus , Vacunas contra Papillomavirus , Medios de Comunicación Sociales , Humanos , Estudios Transversales , Femenino , Adolescente , China , Vacunas contra Papillomavirus/administración & dosificación , Infecciones por Papillomavirus/prevención & control , Niño , Madres/psicología , Adulto , Vacunación/psicología , Conocimientos, Actitudes y Práctica en Salud , Núcleo Familiar , Aceptación de la Atención de Salud , Persona de Mediana Edad , Encuestas y CuestionariosRESUMEN
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 , Clorofenoles , Microextracción en Fase Sólida , Espectrometría de Masa por Ionización de Electrospray , Triclosán , Animales , Microextracción en Fase Sólida/métodos , Triclosán/análisis , Triclosán/química , Carbanilidas/análisis , Ratones , Clorofenoles/análisis , Espectrometría de Masa por Ionización de Electrospray/métodos , Flúor/química , Estructuras Metalorgánicas/química , Límite de Detección , MasculinoRESUMEN
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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Insecticidas , Lesión Pulmonar , FN-kappa B , Neonicotinoides , Nitrocompuestos , Fosfatidilinositol 3-Quinasas , Proteínas Proto-Oncogénicas c-akt , Transducción de Señal , Receptor Toll-Like 4 , Animales , Neonicotinoides/toxicidad , Nitrocompuestos/toxicidad , Ratones , Lesión Pulmonar/inducido químicamente , Transducción de Señal/efectos de los fármacos , Fosfatidilinositol 3-Quinasas/metabolismo , FN-kappa B/metabolismo , Proteínas Proto-Oncogénicas c-akt/metabolismo , Insecticidas/toxicidad , Receptor Toll-Like 4/metabolismo , Pulmón/efectos de los fármacos , Pulmón/patologíaRESUMEN
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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Andrógenos , Límite de Detección , Microextracción en Fase Sólida , Espectrometría de Masa por Ionización de Electrospray , Microextracción en Fase Sólida/métodos , Espectrometría de Masa por Ionización de Electrospray/métodos , Humanos , Andrógenos/sangre , Andrógenos/análisis , Andrógenos/química , Femenino , Estructuras Metalorgánicas/química , Reproducibilidad de los ResultadosRESUMEN
Development of metal-free nanozymes has raised concern for their extensive applications in photocatalysis and sensing fields. As novel metal-free nanomaterials, covalent organic frameworks (COFs) have engendered intense interest in the construction of nanozymes due to their structural controllability and molecular functionality. The formation of the molecular arrangement by embedding orderly donor-acceptors (D-A) linked in the framework topology to modulate material properties for highly efficient enzyme mimicking activity is of importance but challenging. Here, a strong D-A type of COF was designed and synthesized by integrating electron donor units (pyrene) and electron acceptor units (phenanthroline), named Py-PD COF. Using experiments and theoretical calculations, the introduction of a phenanthroline ring endowed the Py-PD COF with a narrowed band gap, and efficient charge transfer and separation. Further, the Py-PD COF exhibited a superior light-responsive oxidase-mimicking characteristic under visible light irradiation, which could catalyze the oxidation of 3,3',5,5-tetramethylbenzidine (TMB) and give the corresponding evolution of color. The nanoenzymatic activity of the Py-PD COF was light-regulated, which offers a fascinating advantage because of its high efficiency and spatial controllability. Based on previously mentioned characteristics, an "on-off" sensing platform for the colorimetric analysis of isoniazid (INH) could be constructed with a good linear relationship (2-100 µM) and a low limit of detection (1.26 µM). This research shows that not only is Py-PD COF an environmentally friendly compound for the colorimetric detection of INH, but it is also capable of providing the interesting D-A type COF-based material for designing an excellent nanozyme.
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Colorimetría , Isoniazida , Estructuras Metalorgánicas , Fenantrolinas , Colorimetría/métodos , Estructuras Metalorgánicas/química , Fenantrolinas/química , Isoniazida/química , Isoniazida/análisis , Procesos Fotoquímicos , Luz , Nanoestructuras/química , Tamaño de la Partícula , Catálisis , Estructura MolecularRESUMEN
This study investigated the influences of mother-daughter communication and social media on mothers' HPV vaccine refusal for their daughters aged 9-17. A cross-sectional online survey among 11,728 mothers of girls aged 9-17 in Shenzhen, China was implemented between July and October 2023. Multi-level logistic regression models were fitted. Among 11,728 participants, 43.2% refused to have their daughters receive an HPV vaccination. In multivariate analysis, more openness in the mother-daughter communication (AOR: 0.99, 95%CI: 0.98, 0.99), perceived more positive outcomes of mother-daughter communication (AOR: 0.77, 95%CI: 0.75, 0.79), higher frequency of exposure to testimonials about daughters' HPV vaccination (AOR: 0.81, 95%CI: 0.78, 0.85) and information encouraging parents to vaccinate their daughters against HPV on social media (AOR: 0.76, 95%CI: 0.73, 0.79), and thoughtful consideration of the veracity of the information specific to HPV vaccines (AOR: 0.80, 95%CI: 0.77, 0.83) were associated with lower vaccine refusal. Mothers who were not the main decision-makers of daughters' HPV vaccination (AOR: 1.28 to 1.46), negative outcome expectancies of mother-daughter communication (AOR: 1.06, 95%CI: 1.04, 1.08), and mothers' HPV vaccine refusal (AOR: 2.81, 95%CI: 2.58, 3.06) were associated with higher vaccine refusal for their daughters. The level of mothers' HPV vaccine refusal for their daughters was high in China. Openness and outcome expectancies of mother-daughter communication and information exposure on social media were considered key determinants of HPV vaccine refusal for daughters. Future HPV vaccination programs should consider these interpersonal factors.
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Infecciones por Papillomavirus , Vacunas contra Papillomavirus , Medios de Comunicación Sociales , Femenino , Humanos , Madres , Estudios Transversales , Núcleo Familiar , Infecciones por Papillomavirus/prevención & control , China , ComunicaciónRESUMEN
China started to offer human papillomavirus (HPV) vaccines to females aged 9-45 years in 2016. However, there was a lack of reports about HPV vaccination coverage in a representative sample of females in China. Therefore, this study aimed to examine the current HPV coverage and associated factors among females aged 9-50 years in Shenzhen, China, based on administrative health records kept by community health centers. A multistage random sampling approach was used. The research team randomly selected 18 community health centers in Shenzhen, and 3118 health records of females aged 9-50 years were then randomly selected from these health centers. Among all participants, 18.7% received at least one dose of HPV vaccination. The highest coverage was observed among females aged 18-26 years (23.4%), followed by those aged 27-35 years (22.0%) and 36-45 years (20.2%). Such coverage was very low among females aged 9-17 years (4.6%) and those aged 46-50 years (3.2%). Among females aged 18 years or above, higher education level, having a family doctor, and permanent residency in Shenzhen were associated with higher HPV vaccination coverage, while older age and being married/divorced were negatively associated with coverage. The HPV vaccination coverage in Shenzhen was 18.7% and there is a strong need for improvement.
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Metabolic analysis in biofluids based on laser desorption/ionization mass spectrometry (LDI-MS), featuring rapidity, simplicity, small sample volume and high throughput, is expected to be a powerful diagnostic tool. Nevertheless, the signals of most metabolic biomarkers obtained by matrix-assisted LDI-MS are too limited to achieve a highly accurate diagnosis due to serious background interference. To address this issue, nanomaterials have been frequently adopted in LDI-MS as substrates. However, the "trial and error" approach still dominates the development of new substrates. Therefore, rational design of novel LDI-MS substrates showing high desorption/ionization efficiency and no background interference is extremely desired. Herein, four few-layered organic metal chalcogenides (OMCs) were precisely designed and for the first time investigated as substrates in LDI-MS, which allowed a favorable internal energy and charge transfer by changing the functional groups of organic ligands and metal nodes. As a result, the optimized OMC-assisted platform satisfyingly enhanced the mass signal by ≈10 000 fold in detecting typical metabolites and successfully detected different saccharides. In addition, a high accuracy diagnosis of central precocious puberty (CPP) with potential biomarkers of 12 metabolites was realized. This work is not only expected to provide a universal detection tool for large-scale clinical diagnosis, but also provides an idea for the design and selection of LDI-MS substrates.
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Given continuous developments in industrial and scientific research, the separation and analysis of complex systems with high sensitivity, throughput, and selectivity is facing new challenges. Chromatography plays an irreplaceable role in separation science and is widely applied in environmental monitoring, pharmaceutical analysis, and food safety. Owing to their outstanding advantages, such as high loading capacity, precise quantification, and good reproducibility, chromatographic separation techniques based on various retention mechanisms have been utilized to detect different analytes. The stationary phase is the core material of chromatographic columns and has an extremely important influence on their separation performance. The selectivity and efficiency of separation largely depend on the chromatographic stationary phase. However, traditional stationary phases, such as silicon-based matrices, are characterized by complex preparation processes, poor permeability, large mass transfer resistance, and a narrow pH range. In addition, polymer matrices show poor mechanical stability and susceptibility to swelling, which limit their applications in the field of separation. Therefore, the development of novel stationary phases with the advantages of traditional stationary phases has become a research emphasis in the field of analytical science in efforts to meet separation requirements under different environments. Various stationary phases based on novel porous materials, such as metal organic frameworks (MOFs), porous organic cages (POCs), and covalent organic frameworks (COFs), are used for chromatographic separation. As mesh crystalline porous materials, MOFs have the advantages of a large surface area, adjustable structure, and easy functionalization; thus, they are widely used as chromatographic stationary phases in reverse-phase chromatography, hydrophilic-mode chromatography, mixed-mode chromatography, and other separation modes. However, because the pore size of MOFs is small and most MOFs demonstrate poor chemical stability under acidic or alkaline conditions, their applications in chromatographic separation are greatly limited. COFs are porous, crystalline polymer materials composed of light elements (H, O, C, N, B, and Si) connected via covalent bonds. Their advantages include a low density, large specific surface area, high porosity, good chemical and thermal stability, regular pores, and adjustable pore sizes. Because of their unique structures and properties, COFs are widely used in many fields such as catalysis, enrichment, gas capture, and sensing. COF materials are also suitable for separation analysis and considered ideal materials for novel chromatographic stationary phases. This review summarizes the latest research progress on the preparation and applications of COF-based chromatographic stationary phases over the past five years. First, the preparation of COF-based stationary phases (SiO2@COFs stationary phase, COFs monolithic stationary phase, pure COFs stationary phase and COFs-coated stationary phase) is introduced. The latest applications of COF-based stationary phases in the separation of organic compounds, isomers, and chiral compounds are then described in detail. Finally, the future development trends and challenges of chromatographic stationary phases based on COFs are discussed to provide new ideas for the future design and development of novel chromatographic stationary phases based on COFs.
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Analysis of cis-diol compounds is essential, because they play important roles in cosmetics, food, pharmaceuticals, and living organisms. Herein, we describe the development of a matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) method to analyse cis-diol compounds. In this method, a 6-borono-1-methylquinoline-1-ium (BMQI) reactive matrix was designed for in situ derivatisation of cis-diol compounds based on the boronate affinity interaction between boronic acid and cis-diol groups. Compared to traditional commercial matrices and other boronic acid reagents, BMQI can significantly accelerate the desorption/ionisation process, improve reproducibility, exhibit free background interference, and enhance signal intensity in the analysis of various cis-diol compounds even for amounts as low as 1 nmol. The BMQI-assisted laser desorption/ionisation mass spectrometry (LDI-MS) was successfully applied to the rapid screening and identification of sugar alcohols in different sugar-free foods. This work provides an alternative method to the LDI-MS analysis of cis-diol-containing molecules, and the method can be extended to other food samples and biofluids.
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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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Estructuras Metalorgánicas , Espectrometría de Masas en Tándem , Animales , Ratones , Espectrometría de Masas en Tándem/métodos , Estructuras Metalorgánicas/química , Cromatografía Líquida de Alta Presión , Extracción en Fase Sólida/métodos , Adsorción , Límite de DetecciónRESUMEN
Oil contamination and industrial organic pollutants emission have been a serious problem affecting the ecological and residential environment. Membrane-based separation shows great application prospect due to its low-cost, environmental-friendly and easy operation. Therefore, the development of efficient oil-water separation membranes is highly desirable. Herein, a fabric filter with superwettability was prepared by coating urchin-like fluorinated covalent organic frameworks (COFs) on fabric, which was well utilized in filtering immiscible oil-water mixture and surfactant-stabilized water-in-oil emulsion driven only by gravity for the first time. The as-prepared COF fabric filter (defined as fabric@u-FCOF) possessed many outstanding properties, including superhydrophobicity with the water contact angle of approximately 151.6°, satisfactory resistance for alkaline, acidic and saline environments, as well as superior mechanical durability under harsh conditions. Because of the super-micropore of fabric@u-FCOF and the nanopore in the COF coating, the obtained fabric@u-FCOF exhibited excellent performances in terms of separation efficiency and permeability, in which the oil flux was up to 16964 L·m-1·h-2 and separation efficiency for the mixed o-dichlorobenzene/water was higher than 99.4%. In addition, the fabric@u-FCOF also showed excellent self-cleaning performance due to the micro/nano hierarchical structure of its surface. These excellent properties make it an ideal candidate for applications of oil/water separation and water purification.
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Triclosan (TCS), an antimicrobial compound, is known to have potential endocrine-disruptive properties, but the underlying toxic mechanisms at the metabolic level are not well understood. Here, we applied metabolomics and lipidomics combined with mass spectrometry imaging (MSI) to unveil the mechanisms of the enhanced growth of MCF-7 breast cancer cell spheroids (CCS) exposed to TCS. To obtain a wide coverage of metabolites and lipids by using MSI, we used techniques of matrix-assisted laser desorption/ionization (MALDI) and MALDI coupled with laser-postionization. The results showed that TCS and TCS sulfate penetrated into the entire area at 0-3 h and both localized in the inner area at 6 h. After 24 h, a portion of two compounds was released from CCS. Omic data indicated that TCS exposure induced alterations via several pathways, including energy metabolism and biosynthesis of glycerophospholipids and glycerolipids. Further MSI data revealed that the enhancement of energy supply in the peripheral area and the increase of energy storage in the inner area might contribute to the enhanced growth of MCF-7 breast CCS exposed to TCS. This study highlights the importance of integrating metabolite distributions and metabolic profiles to reveal the novel mechanisms of TCS-triggered endocrine disrupting effects.
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Neoplasias de la Mama , Triclosán , Humanos , Femenino , Triclosán/toxicidad , Lipidómica , Metabolómica/métodos , Metaboloma , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodosRESUMEN
Lipids and metabolites are small biological molecules that act major roles in cellular functions. Multicellular tumor spheroids (MCTS) are a highly beneficial three-dimensional cellular model for cancer research due to their ability to imitate numerous characteristics of tumor tissues. Increasing studies have performed spatial lipidomics and metabolomics in MCTS using matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). However, these approaches often lack the sensitivity and specificity to offer a comprehensive characterization of lipids and metabolites within MCTS. In this study, we addressed this challenge by utilizing MALDI combined with laser-induced postionization (MALDI-2) and trapped ion mobility spectrometry (TIMS) imaging in H295R adrenocortical MCTS. Our results showed that MALDI-2 could detect more lipids and metabolites in MCTS than the traditional MALDI. TIMS data revealed a successful separation of many isomeric and isobaric ions of lipids and metabolites with different locations (e.g., proliferative region and necrotic region) within MCTS, suggesting an enhanced peak capacity for spatial lipidomics and metabolomics. To further identify these isomeric and isobaric ions, we performed MS/MS imaging experiments to compare the differences in signal intensities and spatial distributions of product ions. Our data highlight the strong potential of MALDI-2 and TIMS imaging for analyzing lipids and metabolites in MCTS, which may serve as valuable tools for numerous fields of biological and medical research.
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Lipidómica , Neoplasias , Humanos , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodos , Lípidos/química , Espectrometría de Masas en Tándem , Metabolómica/métodos , Iones/químicaRESUMEN
Glutathione peroxidase 4 (GPx4) is the membrane peroxidase in mammals that is essential for protecting cells against oxidative damage and critical for ferroptosis. However, no live cell probe is currently available to specifically label GPx4. Herein, we report both inhibitory and noninhibitory fluorescent turn-on probes for specific labeling of GPx4 in live cells. With these probes, the GPx4 expression levels and degradation kinetics in live cells could be visualized, and their real-time responses to the cellular selenium availability were revealed. These probes could also potentially serve as staining reagents to predict the sensitivity of GPx4-related ferroptosis drugs. In view of these features, these GPx4-selective probes will offer opportunities for a deeper understanding of GPx4 function in natural habitats and hold great promise for biomedical applications.
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Colorantes Fluorescentes , Humanos , Células HEK293 , Supervivencia Celular , Fosfolípido Hidroperóxido Glutatión Peroxidasa/metabolismo , Colorantes Fluorescentes/química , Selenio/metabolismoRESUMEN
Tricyclic antidepressants (TCAs) including amitriptyline (AT), doxepin (DOX) and nortriptyline (NT) are the first-line drugs for the clinical treatment of depression; however, monitoring TCA concentrations in biological fluids and tissues is necessary to improve therapeutic effect and determine the cause of death in patients. It is of great significance to develop a rapid and sensitive method for real-time monitoring of TCAs in various biosamples. In this work, we fabricated a novel covalent organic framework (COF) based solid-phase microextraction (SPME) probe by an in-situ step-by-step strategy, which was obtained by sequentially modifying 1,3,5-tri (4-aminophenyl) benzene (TPB) and 2, 5-divinylbenzaldehyde (DVA) on the surface of polydopamine layer. The TPB-DVA-COF-SPME probe possessed high specific surface area (1244 m2·g - 1), regular pores (3.23 nm), good hydrophobicity and stability, resulting in efficient enrichment for TCAs. Furthermore, the combination of TPB-DVA-COF-SPME probe and ambient electrospray ionization mass spectrometry system (ESI/MS) was firstly proposed for rapid and sensitive determination of TCAs in biosamples. As a result, the developed method exhibited low limits of detection (LODs) (0.1-0.5 µgâL - 1), high enrichment factors (39-218), and low relative standard deviations (RSDs) for one probe (1.2-3.8%) and probe-to-probe (2.0-3.7%). Benefiting from these outstanding performance, TPB-DVA-COF-SPME probe was further successfully applied to biosamples (i.e., serum, liver, kidney, and brain) with excellent reusability, indicating the promising applicability of the TPB-DVA-COF-SPME-ESI/MS as a powerful tool for drug monitoring.
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Antidepresivos Tricíclicos , Estructuras Metalorgánicas , Humanos , Antidepresivos Tricíclicos/análisis , Espectrometría de Masa por Ionización de Electrospray/métodos , Acero Inoxidable/química , Microextracción en Fase Sólida/métodos , AgujasRESUMEN
Highly efficient extraction of glycopeptides prior to mass spectrometry detection is extremely crucial for glycoproteomic research, especially in disease biomarker research. Reported here is the first time by applying two-dimensional (2D) covalent organic framework (COFs) nanosheets for highly efficient enrichment of glycopeptides. Particularly, by incorporating hydrophilic monomers through a bottom-up strategy, the 2D COF nanosheets (denoted as NUS-9) displayed an ultra-high graft density of sulfonic groups and super-hydrophilicity. In addition, because of the large surface area, low steric hindrance, high chemical stability, and abundant accessibility sites of 2D COF nanosheets, NUS-9 exhibited remarkable efficiency for glycopeptide enrichment, involving excellent detection sensitivity (0.01 fmol µL-1), outstanding enrichment capability, and good enrichment selectivity (1:1500, horseradish peroxidase (HRP) tryptic digest to bovine serum albumin (BSA) tryptic digest), and recovery (92.2 ± 2.0%). Moreover, the NUS-9 was able to unambiguously detect 631 endogenous glycopeptides from human saliva, demonstrating an unparalleled high efficiency in glycopeptide enrichment. Gene ontology analyses of proteins from human saliva enriched by NUS-9 demonstrated its potential for comprehensive glycoproteome analysis.
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Estructuras Metalorgánicas , Humanos , Estructuras Metalorgánicas/química , Glicopéptidos/química , Espectrometría de Masas , Interacciones Hidrofóbicas e Hidrofílicas , Peroxidasa de Rábano Silvestre/químicaRESUMEN
Enzyme immobilization is critical to boosting its application in various areas. Covalent organic frameworks (COFs) are ideal hosts for enzyme immobilization due to their porous and predesignable structures. Nevertheless, the construction of COFs-based enzyme immobilization systems with high activity via existing immobilization methods (including covalent linkages and channel entrapment) remains a considerable challenge. Herein, a versatile approach was introduced to encapsulate enzymes within hollow COF capsule (named enzyme@COF) using metal-organic frameworks (including ZPF-1(C8H11N4O4.5Zn), ZIF-8(C8H10N4Zn), and ZIF-90(C8H6N4O2Zn)) as sacrificial templates. The obtained porous COF capsule could not only facilitate the efficient mass transfer of enzymatic reactions but also protect enzymes against the incompatible conditions, resulting in enhanced activity and stability of the encapsulated enzymes. Moreover, this approach offered an opportunity to spatially organize multienzymes in COF capsule to construct enzyme cascade system. For instance, glucose oxidase (GOx) and cytochrome c (Cyt c) were coencapsulated within COF capsule to construct GOx-Cyt c cascade. The integration of GOx and Cyt c within COF capsule achieved â¼1.6-fold improvement in catalytic activity than that of free enzymes and the resultant GOx-Cyt c@COF was successfully adopted as a nanoreactor for the sensitive determination of glucose in serum. This work provided a new insight into the design of COFs-based enzyme immobilization systems.
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A hollow microtubular covalent organic framework (denoted as TatDha-COF) was synthesized by solvothermal method for the enrichment and determination of quinones. The TatDha-COF showed large specific surface area (2057 m2 g-1), good crystal structure, ordered pore size distribution (2.3 nm), stable chemical properties and good reusability. Accordingly, a simple and efficient method based on dispersive solid-phase extraction (d-SPE) and atmospheric pressure gas chromatography tandem mass spectrometry (APGC-MS/MS) was developed for the determination of quinones in complex samples. The established method demonstrated a wide liner range, good linearity (r>0.9990), high enrichment factors (EFs, 24-69-folds) and low detection limits (LODs, 0.200-30.0 pg L-1, S/N≥3). On this basis, the suggested method was successfully applied to sensitively detect the eight ultratrace quinones in mice plasma. Overall, the established method has provided a powerful tool for the enrichment and detection of ultratrace quinones in complex samples, presenting the promising application of TatDha-COF in sample pretreatment.