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Immune cell function depends on specific metabolic programs dictated by mitochondria, including nutrient oxidation, macromolecule synthesis, and post-translational modifications. Mitochondrial adaptations have been linked to acute and chronic inflammation, but the metabolic cues and precise mechanisms remain unclear. Here we reveal that histone deacetylase 3 (HDAC3) is essential for shaping mitochondrial adaptations for IL-1ß production in macrophages through non-histone deacetylation. In vivo, HDAC3 promoted lipopolysaccharide-induced acute inflammation and high-fat diet-induced chronic inflammation by enhancing NLRP3-dependent caspase-1 activation. HDAC3 configured the lipid profile in stimulated macrophages and restricted fatty acid oxidation (FAO) supported by exogenous fatty acids for mitochondria to acquire their adaptations and depolarization. Rather than affecting nuclear gene expression, HDAC3 translocated to mitochondria to deacetylate and inactivate an FAO enzyme, mitochondrial trifunctional enzyme subunit α. HDAC3 may serve as a controlling node that balances between acquiring mitochondrial adaptations and sustaining their fitness for IL-1ß-dependent inflammation.
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Ácidos Grasos/metabolismo , Histona Desacetilasas/metabolismo , Inflamación/metabolismo , Interleucina-1beta/metabolismo , Mitocondrias/metabolismo , Adulto , Animales , Caspasa 1/metabolismo , Femenino , Humanos , Inflamación/patología , Metabolismo de los Lípidos , Masculino , Ratones Endogámicos C57BL , Ratones Noqueados , Persona de Mediana Edad , Mitocondrias/ultraestructura , Subunidad alfa de la Proteína Trifuncional Mitocondrial/metabolismo , Células Mieloides/metabolismo , Proteína con Dominio Pirina 3 de la Familia NLR/metabolismo , Oxidación-Reducción , Fosforilación Oxidativa , Adulto JovenRESUMEN
Activated macrophages adapt their metabolic pathways to drive the pro-inflammatory phenotype, but little is known about the biochemical underpinnings of this process. Here, we find that lipopolysaccharide (LPS) activates the pentose phosphate pathway, the serine synthesis pathway, and one-carbon metabolism, the synergism of which drives epigenetic reprogramming for interleukin-1ß (IL-1ß) expression. Glucose-derived ribose and one-carbon units fed by both glucose and serine metabolism are synergistically integrated into the methionine cycle through de novo ATP synthesis and fuel the generation of S-adenosylmethionine (SAM) during LPS-induced inflammation. Impairment of these metabolic pathways that feed SAM generation lead to anti-inflammatory outcomes, implicating SAM as an essential metabolite for inflammatory macrophages. Mechanistically, SAM generation maintains a relatively high SAM:S-adenosylhomocysteine ratio to support histone H3 lysine 36 trimethylation for IL-1ß production. We therefore identify a synergistic effect of glucose and amino acid metabolism on orchestrating SAM availability that is intimately linked to the chromatin state for inflammation.
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Histonas/metabolismo , Macrófagos Peritoneales/metabolismo , S-Adenosilmetionina/metabolismo , Adenosina Trifosfato/metabolismo , Adulto , Animales , Femenino , Humanos , Inflamación/inducido químicamente , Inflamación/metabolismo , Inflamación/patología , Interleucina-1beta/metabolismo , Lipopolisacáridos/toxicidad , Macrófagos Peritoneales/patología , Masculino , Metilación/efectos de los fármacos , RatonesRESUMEN
Breaking the trade-off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H2 O2 ) photosynthesis, especially the side-on configuration of oxygen (O2 ) on the catalyst surface will cause the cleavage of O-O bonds, which drastically hinders the H2 O2 production performance. Herein, we present an atomically heteroatom P doped ZnIn2 S4 catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar-driven H2 O2 production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn2 S4 at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O-O bonds and reducing the energy barriers to H2 O2 production. As a result, the oxygen adsorption configuration is regulated from side-on (Yeager-type) to end-on (Pauling-type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66â µmol g-1 h-1 . This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.
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The profiling of natural products is important in modern biological sciences and new drug development. However, the separation and characterization of complex herbal extracts are significantly challenging for researchers in the biochemical field. Herein, an offline two-dimensional mixed-mode liquid chromatography × reversed-phase liquid chromatography system is developed. Our system exhibits high orthogonality and is composed of a newly prepared stationary phase in the first dimension and a traditional C18 phase in the second dimension, and is operated in combination with a high-resolution mass spectrometry and molecular network. Sanguisorba officinalis L. is studied using the proposed method owing to its bioactivity. With the aid of orthogonal separation, the ionization of the individual components is improved. The number of detected compounds and separated peaks are significantly increased when one-dimensional liquid chromatography is upgraded to two-dimensional liquid chromatography. In addition, 270 compounds (127 of which are tentatively characterized as new compounds, and further confirmation is needed) are successfully characterized based on their fragmentation patterns under the guidance of molecular network, while only 95 compounds are characterized using one-dimensional liquid chromatography and high-resolution mass spectrometry. The results indicate that the developed offline two-dimensional mixed-mode liquid chromatography × reversed-phase liquid chromatography, tandem high-resolution mass spectrometry, and molecular network method are effective for profiling complex samples.
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Cromatografía de Fase Inversa , Sanguisorba , Cromatografía Líquida de Alta Presión/métodos , Cromatografía Liquida , Espectrometría de Masas en TándemRESUMEN
Carbon dot (CD)-based multi-mode sensing has drawn much attention owing to its wider application range and higher availability compared with single-mode sensing. Herein, a simple and green methodology to construct a CD-based dual-mode fluorescent sensor from the waste biomass of flowers of wintersweet (FW-CDs) for parallel and semi-quantitative visual detection of Cr(VI) and Fe3+ was firstly reported. The FW-CD fluorescent probe had a high sensitivity to Cr(VI) and Fe3+ with wide ranges of linearity from 0.1 to 60 µM and 0.05 to 100 µM along with low detection limits (LOD) of 0.07 µM and 0.15 µM, respectively. Accordingly, the FW-CD-based dual-mode sensor had an excellent parallel sensing capacity toward Cr(VI) and Fe3+ with high selectivity and strong anti-interference capability by co-using dual-functional integration and dual-masking strategies. The developed parallel sensing platform was successfully applied to Cr(VI) and Fe3+ quantitative detection in real samples with high precision and good recovery. More importantly, a novel FW-CD-based fluorescent hydrogel sensor was fabricated and first applied in the parallel and semi-quantitative visual detection of Cr(VI) and ferrous ions in industrial effluent and iron supplements, further demonstrating the significant advantage of parallel and visual sensing strategies.
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Cromo/análisis , Flores/química , Colorantes Fluorescentes , Tecnología Química Verde , Hierro/análisis , Extractos Vegetales/química , Puntos Cuánticos/química , Colorantes Fluorescentes/síntesis química , Colorantes Fluorescentes/químicaRESUMEN
Preparative liquid chromatography has become an important purification method owing to its advantages of high separation efficiency, good reproducibility, and low solvent consumption. Because overloading in preparative liquid chromatography must be performed to increase the throughput in a cycle, nonlinear chromatographic behavior is observed. Therefore, it is crucial to carefully study nonlinear chromatography for the purification of a given product, which facilitates the efficient optimization of the purification parameters. In this work, a method for the development of a purification method using preparative liquid chromatography based on nonlinear chromatography is proposed. Hydroxytyrosol was selected as the subject for method demonstration. Using methanol and ethanol as organic modifiers, the optimum flow rate was determined on three commercial columns entitled C8 TDE, C18 ME, and C18 TDE, respectively. The curves were fitted with the van Deemter equation, with thorough analysis of the A, B, and C terms. Adsorption isotherms were subsequently studied to explore the distribution of solutes between the stationary and mobile phases at equilibrium. C18 TDE, 5 vol% ethanol-water, and 0.2 mL/min were selected as the optimal separation material, elution solvent, and flow rate, respectively. Purification of hydroxytyrosol was tentatively confirmed on a C18 TDE column with 1.6% sample loading, 90.98% recovery, and 98.01% purity.
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Herein, a novel L-arginine (L-Arg)-modified polydopamine (PDA)-coated capillary (PDA/L-Arg@capillary) was firstly fabricated via the basic amino-acid-induced PDA co-deposition strategy and employed to constitute a new chiral ligand exchange capillary electrochromatography (CLE-CEC) method for the high-performance enantioseparation of D,L-amino acids (D,L-AAs) with L-Arg as the immobilized chiral ligand coordinating with the central metal ion Zn(II) as running buffer. Assisted by hydrothermal treatment, the robust immobilization of L-Arg on the capillary inner wall could be facilely achieved within 1 h, prominently improving the synthesis efficiency and simplifying the preparation procedure. The successful preparation of PDA/L-Arg coatings in the capillary was systematically characterized and confirmed using several methods. In comparison with bare and PDA-functionalized capillaries, the enantioseparation capability of the presented CLE-CEC system was significantly enhanced. Eight D,L-AAs were completely separated and three pairs were partially separated under the optimal conditions. The prepared PDA/L-Arg@capillary showed good repeatability and stability. The potential mechanism of the greatly enhanced enantioseparation performance obtained by PDA/L-Arg@capillary was also explored. Moreover, the proposed method was further utilized for studying the enzyme kinetics of L-glutamic dehydrogenase, exhibiting its promising prospects in enzyme assays and other related applications.
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Arginina/química , Electrocromatografía Capilar , Indoles/química , Polímeros/químicaRESUMEN
Metal-organic frameworks (MOFs) have been widely applied in a variety of fields. However, most of the developed MOFs are micrometer scale in crystal size and contain only micropores, which will limit the mass transport and diffusion of various analytes into their internal interaction sites, severely restricting the potential of MOFs in separation science. Herein, nanoscale hierarchically porous MOFs (NHP-MOFs) were first explored as a novel MOF-based stationary phase with excellent mass transfer performance and abundant accessible interaction sites for high-performance chromatographic separation. As a proof-of-concept demonstration, the nanoscale hierarchically micro- and mesoporous UiO-66 (NHP-UiO-66) was firmly immobilized on the capillary inner surface and utilized as the porous stationary phase for high-resolution and high-efficiency electrochromatographic separation. A wide range of low-, medium-, and high-molecular-weight analytes, including substituted benzenes, chlorobenzenes, polycyclic aromatic hydrocarbons, nucleosides, polypeptides, and proteins were all separated well on a NHP-UiO-66-coated column with excellent resolution and repeatability, exhibiting significantly improved column efficiency and separation ability compared to those of a microporous UiO-66-modified column. The maximum column efficiencies for all the six kinds of analytes reached up to 1.2 × 105 plates/m, and the relative standard deviations of the migration times of substituted benzenes for intraday, interday, and column-to-column were all lower than 5.8%. These results reveal that NHP-MOFs can effectively combine the advantages of the high specific surface area of microporous MOFs and the excellent mass transfer performance and abundant accessible interaction sites of NHP materials, possessing great prospect for high-performance chromatographic separation.
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In this work, dried flowers of Osmanthus fragrans Lour. were applied as green precursors to synthesize carbon dots (CDs) by a green hydrothermal method for the first time. The CDs showed strong blue fluorescence at 410 nm under 340-nm excitation with a quantum yield of approximately 18.53%. Furthermore, the CDs were applied for the sensitive detection of Fe3+. The linear response of Fe3+ ranged from 10 nM to 50 µM with a limit of detection as low as 5 nM. In addition, other ions were used as competitive substances to explore the selectivity of CDs for Fe3+. The fluorescence quenching effect of Fe3+ was much stronger, which demonstrated that the CDs had high selectivity for Fe3+ and they can be employed for the selective detection of Fe3+. The potential fluorescence quenching mechanism between CDs and Fe3+ was identified as the inner filter effect. The CDs were then used as a fluorescent sensor for the detection of Fe3+ in water samples and human serum; the recovery range was 93.76-113.80% (relative standard deviation less than 0.79%). These results indicate that the CDs can be applied for the sensitive and selective detection of Fe3+ in real samples. Moreover, on the basis of the redox reaction between Fe3+ and ascorbic acid (AA), the CD-Fe3+ system can be used as a fluorescent "off-on" sensor for the detection of AA with a limit of detection of 5 µM. What is more, because of their low toxicity and biocompatibility, the CDs can also be used for cell imaging and acted as a fluorescent probe for fluorescence imaging of Fe3+ and AA in living cells. These results demonstrate that the CDs have great potential for application in the fields of sensing, bioimaging, and even disease diagnosis.
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Ácido Ascórbico/análisis , Carbono/química , Compuestos Férricos/análisis , Flores/química , Tecnología Química Verde/métodos , Nanopartículas/química , Oleaceae/química , Células A549 , Medios de Cultivo , Humanos , Límite de Detección , Microscopía Electrónica de Transmisión , Espectroscopía de Fotoelectrones , Espectrometría de FluorescenciaRESUMEN
A highly efficient and ecofriendly extraction method using deep eutectic solvents was developed to extract bioactive flavonoids from Abelmoschus manihot (Linn.) Medicus flowers. First, a series of deep eutectic solvents using choline chloride as hydrogen bond acceptor with different hydrogen bond donors was successfully synthesized. Then, the types of deep eutectic solvents and the extraction conditions for bioactive flavonoids (hyperoside, isoquercitrin, and myricetin) were optimized based on the flavonoids extraction efficiencies. The optimized deep eutectic solvent for hyperoside and isoquercitrin extraction was composed of choline chloride and acetic acid with a molar ratio of 1:2. The optimized deep eutectic solvent for myricetin extraction was composed of one mole of choline chloride and two moles of methacrylic acid. The optimal extraction conditions were set as: solid to solvent ratio, 35:1 (mg/mL); extraction time, 30 min; extraction temperature, 30°C. Qualitative and quantitative analysis were performed using ultra high performance liquid chromatography with tandem mass spectrometry and high-performance liquid chromatography. And the extraction efficiencies of hyperoside, isoquercitrin, and myricetin under optimal extraction conditions were calculated as 11.57, 5.64, and 1.11 mg/g, much higher than those extracted by traditional extraction solvents. Therefore, the prepared deep eutectic solvents can be selected as alternative solvent to extract bioactive flavonoids.
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Abelmoschus/química , Fraccionamiento Químico/métodos , Cromatografía Líquida de Alta Presión/métodos , Flavonoides/análisis , Flavonoides/aislamiento & purificación , Extractos Vegetales/análisis , Extractos Vegetales/aislamiento & purificación , Flores/química , Espectrometría de Masas en TándemRESUMEN
A magnetic molecularly imprinted composite was prepared by reverse microemulsion using carbon dots (CDs), Fe3O4 as the co-nucleus, and a molecularly imprinted polymer (MIP; with 2,4,6-trinitrophenol as the template) acting as recognition sites. The composite of type CD/Fe3O4@MIPs was characterized by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), zeta potentiometric analysis, X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The results showed that the composite MIP has a spherical shape with average diameter of 200 nm. They also showed that the composite contains core-shell structures with several Fe3O4 nanoparticles and CDs embedded in each of the microsphere. The composite can extract 2,4,6-trinitrophenol (TNP) and has an imprinting factor of 3.6. It has high selectivity and sensitivity for TNP which acts as a quencher of the fluorescence of the CDs (with excitation/emission maxima at 370/470 nm). The limit of detection of this fluorometric TNP assay is 0.5 nM. The method was successfully applied to the determination of TNP in spiked tap water and river water samples, and recoveries ranged from 89.4% to 108.5% (with an RSD of <6%). Graphical abstract Schematic representation of the magnetic molecularly imprinted composite containing fluorescent carbon dots, Fe3O4 and molecularly imprinted polymer (CD/Fe3O4@MIPs). The CD/Fe3O4@MIPs were applied to the selective and sensitive detection of 2,4,6-trinitrophenol (TNP) by fluorometry.
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A core-shell structured magnetic covalent organic frameworks of the type Fe3O4@COFs was prepared by using the Fe3O4 nanoparticles as magnetic core, and 4,4"-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectrum, Fourier transform infrared spectroscopy, zeta potentiometric analysis, X-ray diffraction, vibrating sample magnetometry, thermogravimetric analysis and the nitrogen adsorption-desorption isotherms. The Fe3O4@COFs have core-shell structure with average diameter of 200 ± 2.4 nm, a high specific surface area (124 m2·g-1), uniform pore size distribution (3.1 nm), good magnetic responsivity (36.8 emu·g-1), good thermal and chemical stability. They were applied as the sorbents for magnetic solid phase extraction (MSPE) for fluoroquinolones (FQs) ciprofloxacin, enrofloxacin, lomefloxacin, gatifloxacin, levofloxacin and pefloxacin. The effects of sorbent dosage, extraction time, p H value, ionic strength, desorption solvent and desorption time were investigated. By combining MSPE with HPLC-DAD analysis, a rapid and sensitive method was developed for the enrichment and determination of these FQs. The method had good linearity in the range of 2.5-1500 ng·g-1 FQ concentration range and low limits of detection (0.25-0.5 ng·g-1). The method was successfully applied to the extraction and determination of FQs in (spiked) pork, milk and human plasma samples. Recoveries ranged from 78.7-103.5% (with RSD<6.2%). Graphical abstract Schematic representation of the magnetic covalent organic frameworks which prepared by using the Fe3O4 nanoparticles as magnetic core, 4,4"-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were applied as adsorbents for magnetic solid phase extraction of six fluoroquinolones (FQs) and HPLC-DAD was applied to analysis the extraction efficiencies.
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BACKGROUND: Antibiotics and none-steroidal anti-inflammatory drugs are often taken orally to treat human diseases. The use of these drugs adversely could affect the natural oral microbiota composition and oral immune system. In the meanwhile, it may break the original balance of oral micro-ecosystem. Exploring this change is of great importance to host health. METHODS: In this study, we took 20 SD rats and divided them into four groups of five rats each. Each of these groups was administered specified doses of amoxicillin (AMX), ornidazole (ORD), aspirin (ASP), or purified water (CTR), using oral gavage daily for 14 days. High-throughput sequencing was used to investigate the microbiota difference in the four groups of rats once the oral gavage completed. ELISA kit was used to determine IgG and SIgA content, to understand the effect of the drugs on the oral immune system. RESULTS: We found that oral bacterial composition, IgG and sIgA were significantly affected by the use of these drugs. No matter which medication the rats takes, oral microbiota diversity increase significantly. At the genus level, The Lactobacillaceae, which is essential to the human food digest, raised in the aspirin take group. Staphylococcus and Pasteurella increased in the ornidazole group. Klebsiella, Corynebacterium rose significantly in the amoxicillin group. In normal oral cavity without taking the task medicine, Streptococcus, Pasteurella, and Rothia were in a relatively high abundance. IgG and SIgA content also changed by using these drugs, thus indicating applied those drugs impact of the oral immune system. CONCLUSION: Our results indicate that antibiotic and none-steroidal anti-inflammatory drugs could influence the oral microbiota composition, which could also destroy the original oral micro-ecosystem environment. The non-antibiotic drug effect on the oral microbiota and oral immune system similar to the antibiotic drug. All these changes may have a negative influence on host health.
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Antibacterianos/farmacología , Antiinflamatorios no Esteroideos/farmacología , Microbiota/efectos de los fármacos , Boca/microbiología , Animales , Biodiversidad , Filogenia , Ratas Sprague-DawleyRESUMEN
Nano-sized molecularly imprinted polymers for tiliroside were successfully prepared by a precipitation polymerization method. Acrylamide, ethylene glycol dimethacrylate, azobisisobutyronitrile, and acetonitrile/dimethyl sulfoxide were used as functional monomer, cross-linker, initiator, and porogen, respectively. The structural features and morphological characterization of tiliroside-imprinted polymers were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The adsorption experiments indicated that the tiliroside-imprinted polymers exhibited high selective recognition property to tiliroside. Scatchard analysis indicated that the homogeneous-binding sites were formed in the polymers. The selectivity test revealed that the adsorption capacity and selectivity of polymers to tiliroside was significantly higher than that of rutin, astragalin, and kaempferol. Finally, the tiliroside-imprinted polymers were employed as adsorbents in solid-phase extraction for the extraction of tiliroside from the ethyl acetate extract of the flowers of Edgeworthia gardneri (wall.) Meisn. The results demonstrated that the extraction recoveries of tiliroside ranged from 69.3 to 73.5% by using tiliroside-imprinted polymers coupled with solid-phase extraction method. These results indicated that the tiliroside-based molecularly imprinted solid-phase extraction method was proven to be an effective technique for the separation and enrichment of tiliroside from natural medicines.
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Flavonoides/aislamiento & purificación , Flores/química , Impresión Molecular , Thymelaeaceae/química , Adsorción , Cromatografía Líquida de Alta Presión , Polímeros , Extracción en Fase SólidaRESUMEN
Mussel-inspired polydopamine (PDA) and its derivative materials have exhibited a huge potential as a facile and versatile route to fabricate multifunctional coatings on virtually any substrate surface. However, their performance and applicability are frequently obstructed by limited optical absorption in visible regions of PDA and poor surface adhesion persistence of dopamine solutions. Herein, we report a facile strategy to improve these problems by rationally regulating the dopamine polymerization pathway through mixed-solvent-mediated periodate oxidation of dopamine. The spectral analysis, ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry, and density functional theory simulations systematically demonstrate that the mixed-solvent reaction systems can effectively accelerate the periodate-induced formation of cyclized moieties in the PDA microstructure and inhibit their further oxidative cleavage, thus contributing to narrowing the inherent energy band gap of PDA and improving the long-lasting surface deposition performance of aged dopamine solutions. Moreover, the newly constructed cyclized species-rich PDA coatings have excellent surface uniformity and significantly enhanced chemical stability. Benefiting from these fascinating properties, they have been further used for permanent dyeing of natural gray hair with remarkably improved blackening effect and excellent practicability, which exhibited their promising prospect in real-world applications.
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Dopamina , Polímeros , Dopamina/química , Solventes , Polímeros/químicaRESUMEN
Sanguisorba officinalis L. (SO), a well-known herbal medicine, has been proven to show effect against thrombocytopenia. However, metabolites of SO in vivo are still unclear, and the underlying mechanism of SO against thrombocytopenia from the aspect of metabolites have not been well elucidated. In this study, an improved analytical method combined with UHPLC-QTOF MS and a molecular network was developed for the rapid characterization of metabolites in vivo based on fragmentation patterns. Then, network pharmacology (NP) was used to elucidate the potential mechanism of SO against thrombocytopenia. As a result, a total of 1678 exogenous metabolites were detected in urine, feces, plasma, and bone marrow, in which 104 metabolites were tentatively characterized. These characterized metabolites that originated from plasma, urine, and feces were then imported to the NP analysis. The results showed that the metabolites from plasma, urine, and feces could be responsible for the pharmacological activity against thrombocytopenia by regulating the PI3K-Akt, MAPK, JAK-STAT, VEGF, chemokine, actin cytoskeleton, HIF-1, and pluripotency of stem cells. This study provides a rapid method for metabolite characterization and a new perspective of underlying mechanism study from the aspect of active metabolites in vivo.
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UiO-66(NH2), a metal-organic framework, exhibits excellent UV absorption and energy transfer performance and can be used as a substrate for surface-assisted laser desorption/ionization (SALDI) analysis of small molecules. Molecularly imprinted polymers (MIPs) exhibit outstanding selectivity toward certain targets. The complexes of UiO-66(NH2) and MIPs can be applied as both an adsorbent and substrate for SALDI-time-of-flight mass spectrometry (SALDI-TOF MS) analysis of small molecules. Herein, magnetic UiO-66(NH2)-molecularly imprinted polymers (MUMIPs) were prepared for the selective enrichment and detection of luteolin via SALDI-TOF MS. The amino group on UiO-66(NH2) were used as functional monomer to prepare MIPs that interact with luteolin via hydrogen bonding. The surface functional monomer can effectively control the coating thickness of the MIPs to avoid embedding template molecules and enhance adsorption performance. In addition, Fe3O4 particles were introduced for rapid magnetic separation. The physicochemical properties of the MUMIPs were characterized via scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, vibrating sample magnetometry, Brunauer-Emmett-Teller analysis, and X-ray photoelectron spectroscopy. Adsorption experiments and selectivity studies indicated that MUMIPs exhibited good adsorption capacity, fast adsorption rates, and excellent luteolin selectivity. MUMIPs are efficient substrates for the SALDI analysis of luteolin and its structural analogs. In addition, the MUMIPs-SALDI-TOF MS method successfully detected luteolin in rat plasma and urine after administration of oral Chrysanthemum morifolium Ramat extracts. This method possessed high sensitivity with a limit of detection of 0.5 ng/mL. The traditional precipitation method combined with high-performance liquid chromatography-mass spectrometry was also used to analyze luteolin in biological samples. Compared with the traditional method, the novel MUMIP-SALDI-TOF MS method can more effectively detect the target compounds in complex samples. Ultimately, the MUMIP-SALDI-TOF MS method was applied to detect luteolin and its metabolites in rat liver after oral luteolin treatment. Three luteolin metabolites (apigenin, chrysoeriol, and diosmetin) were analyzed using the newly developed MUMIP-SALDI-TOF MS method.
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Estructuras Metalorgánicas , Impresión Molecular , Adsorción , Animales , Rayos Láser , Luteolina/química , Fenómenos Magnéticos , Espectrometría de Masas , Polímeros Impresos Molecularmente , Ácidos Ftálicos , Polímeros/química , RatasRESUMEN
Magnetic porous cellulose molecularly imprinted polymers-based bisphenols have been developed using Fe3O4 as the magnetic material, a deep eutectic solvent as the assisted solvent, and N-isopropylacrylamide as the functional monomer. The resulting magnetic porous cellulose molecularly imprinted polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometry, thermal gravimetric analysis, and Brunauer-Emmett-Teller analysis. Moreover, the adsorption properties of the magnetic porous cellulose molecularly imprinted polymers toward bisphenol A, bisphenol F, and bisphenol AF were investigated using static, dynamic, and selective adsorption experiments. The introduction of porous cellulose materials significantly improves the capabilities of the material. The adsorption capacity, mass transfer efficiency, and selectivity of the magnetic porous cellulose molecularly imprinted polymers toward bisphenol A were 5.9, 4.0, and 4.4 times those of traditional molecularly imprinted polymers. Moreover, the adsorption stability of the magnetic porous cellulose molecularly imprinted polymers was investigated under different temperature and pH conditions. The adsorption characteristics of the magnetic porous cellulose molecularly imprinted polymers toward the target molecules were investigated using adsorption isotherm, kinetic, and thermodynamic models. Hydrogen bonding is the main interaction formed between the magnetic porous cellulose molecularly imprinted polymers and the target molecules. Magnetic porous cellulose molecularly imprinted polymers have great application value with excellent stability and reusability. Finally, the combination of the magnetic porous cellulose molecularly imprinted polymers and high-performance liquid chromatography or ultra-performance liquid chromatography-mass spectrometry was successfully used for the purification and detection of bisphenols in milk (1.349 ng/mL bisphenol F and 3.014 ng/mL bisphenol AF), canned fruits (1129 ng/mL bisphenol A, 10.11 ng/mL bisphenol F, and 91.87 ng/mL bisphenol AF), and fish (11.91 ng/mL bisphenol AF) samples. Furthermore, the magnetic porous cellulose molecularly imprinted polymer method is more selective, sensitive, and accurate than the traditional precipitation method.
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Impresión Molecular , Adsorción , Animales , Compuestos de Bencidrilo , Celulosa , Disolventes Eutécticos Profundos , Fenómenos Magnéticos , Polímeros Impresos Molecularmente , Fenoles , Polímeros/química , Porosidad , Solventes/químicaRESUMEN
The low-usage of solar energy and the sluggish separation efficiency of the photogenerated electrons/holes pairs are the obstacles in the practical application of photocatalysts. The integration of upconversion and Z-scheme heterojunction is expected to break the barriers to achieve the efficient charge separation and broaden near-infrared light absorption. Herein, an effective indirect Z scheme AgInS2/In2S3 heterostructure with carbon quantum dots (CQDs, as the electron conduction medium) and Lu3NbO7:Yb, Ho (as upconversion function) has been successfully synthesized. Consequently, the Lu3NbO7: Yb, Ho/CQDs/AgInS2/In2S3 heterostructure exhibited superior photocatalytic activities for Cr(VI) reduction and H2O2 production, reducing 99.9% of Cr(VI)(20 ppm, 15 min) and 78.5% of Cr(VI) (40 ppm, 30 min) with visible light irradiation as well as 94.0% of Cr(VI) (20 ppm, 39 min) under NIR light irradiation. Simultaneously, the heterostructure could generate 902.9 µM H2O2 for 5 h under visible light irradiation. The intensive photocatalytic properties could primarily be attributed to the boosted light absorption capacity, the improved solar-to-energy conversion by the remarkable upconversion capacity of Lu3NbO7: Yb, Ho/CQDs and the faster charge transfer through a Z-schematic pathway. This work is anticipated to open a novel "window" for designing the efficient photocatalysts by coupling of Lu3NbO7: Yb, Ho and CQDs.
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Peróxido de Hidrógeno , Puntos Cuánticos , Carbono , Catálisis , LuzRESUMEN
The NLRP3 (NOD-, LRR- and pyrin domain-containing protein 3) inflammasome plays a pivotal role in defending the host against infection as well as sterile inflammation. Activation of the NLRP3 inflammasome is critically regulated by a de-ubiquitination mechanism, but little is known about how ubiquitination restrains NLRP3 activity. Here, we showed that the membrane-bound E3 ubiquitin ligase gp78 mediated mixed ubiquitination of NLRP3, which inhibited NLRP3 inflammasome activation by suppressing the oligomerization and subcellular translocation of NLRP3. In addition, the endoplasmic reticulum membrane protein insulin-induced gene 1 (Insig-1) was required for this gp78-NLRP3 interaction and gp78-mediated NLRP3 ubiquitination. gp78 or Insig-1 deficiency in myeloid cells led to exacerbated NLRP3 inflammasome-dependent inflammation in vivo, including lipopolysaccharide-induced systemic inflammation and alum-induced peritonitis. Taken together, our study identifies gp78-mediated NLRP3 ubiquitination as a regulatory mechanism that restrains inflammasome activation and highlights NLRP3 ubiquitination as a potential therapeutic target for inflammatory diseases.