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As a kind of promising oxygen evolution reaction (OER) catalysts, metal-organic frameworks (MOF) are often constrained by their inherent poor electroconductivity and structural instability. In this study, we developed a mono-dispersed zeolitic imidazolate framework-67@cuprous oxide (ZIF-67@Cu2O) core-shell catalyst via in-situ growth method for highly efficient alkaline OER. The ZIF-67@Cu2O shows an excellent OER activity with a low overpotential of 254 mV at 10 mA cm-2 and Tafel slope of 87.9 mV·dec-1 in 1.0 M KOH. Furthermore, the ZIF-67@Cu2O also shows a high turnover frequency (TOF) of 0.166 s-1 at 1.60 V vs. RHE and long-term stability for 160 h at a high current density of 100 mA cm-2. The unique core-shell structure with the Cu2O core linked with ZIF-67 shell through interfacial di-oxygen bridge improves the structural stability, enhances the charge transfer, and provides more active sites. Moreover, the interfacial coordination structure was regulated from Co-N4 to Co-N2O2 which elevates the valence of Co sites and optimizes the adsorption free energy of oxygen-containing intermediates, thus improving the electrocatalytic OER performance. This work could propose the way for designing novel MOF-based nanomaterials and developing desirable and robust heterogeneous OER catalysts.
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In this study, zeolitic imidazolate framework 8 (ZIF-8) was coated on porous Ti6Al4V scaffolds, either bare or previously modified using hydroxyapatite (HA) or HA and gelatin (HAgel), via a growing single-step method in aqueous media using two contact times at 6 h and 24 h. The coated scaffolds termed ZIF-8@Ti, ZIF-8@HA/Ti, and ZIF-8@HAgel/Ti were characterized via scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and molecular plasma-atomic emission spectroscopy (MP-AES). In order to assess the cell proliferation rate, the cytocompatibility of the scaffolds was evaluated in primary osteoblasts (hOBs) using alamarBlue assay, while the osteoconductivity was analyzed in hOBs using a real-time approach, evaluating the expression of secreted phosphoprotein 1 (SPP1). Osteopontin, which is the protein encoded by this gene, represents the major non-collagenous bone protein that binds tightly to HA. The scaffolds were shown to be non-cytotoxic based on hOB proliferation at all time points of analysis (24 h and 72 h). In hOB cultures, the scaffolds induced the upregulation of SPP1 with different fold changes. Some selected scaffolds were assayed in vitro for their antibacterial potential against Staphylococcus epidermidis; the scaffolds coated with ZIF-8 crystals, regardless of the presence of HA and gelatin, strongly inhibited bacterial adhesion to the materials and reduced bacterial proliferation in the culture medium, demonstrating the suitable release of ZIF-8 in a bioactive form. These experiments suggest that the innovative scaffolds, tested herein, provide a good microenvironment for hOB adhesion, viability, and osteoconduction with effective prevention of S. epidermidis adhesion.
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Background: A successful immune response against tumors depends on various cellular processes. Hence, there is an urgent need to construct a proficient nanoplatform for immunotherapy that can concurrently regulate the activities of various cells participating in the immune process. We have developed zeolitic imidazolate framework-8 (ZIF-8) formula, with good pH sensitivity, which is conducive to the release of drugs in the tumor site (acidic environment) and significantly improves immunotherapy. This is achieved through the coordinated action of different therapeutic agents, such as the photothermal agent polydopamine (PDA), the chemodrug camptothecin (CPT), and the immunomodulator 1-methyl-D-tryptophan (1-MT). Materials and Methods: In this study, we evaluated the antitumor effect of PDA/(CPT + 1-MT) @ZIF-8 (PCMZ) nanoparticles (NPs) in vitro and in vivo and investigated the molecular mechanism of PCMZ NPs in tumor suppression via photothermal-chemo-immunotherapy. Results: MTT and Annexin V-FITC/PI double staining apoptosis test showed that PCMZ NPs could induce apoptosis of 4T1 cell, and PCMZ NPs could cause 4T1 cell necrosis under 808 nm laser irradiation. The objective is to establish a unilateral breast cancer model in mice and investigate the effect of PCMZ NPs on tumor growth and tumor suppression in tumor bearing mice. The results showed that PCMZ NPs showed good heating effect in vivo and effectively inhibited tumor growth under 808 nm laser irradiation. In addition, PCMZ NPs could induce the immunogenic death of tumor cells, promote the maturation of DCs, inhibit IDO pathway, and finally differentiate T cells into cytotoxic T cells and helper T cells, so as to effectively activate the anti-tumor immune response. Conclusion: The PCMZ NPs, possessing good photothermal conversion capabilities due to join of PDA, effectively overcome two main challenges in immunotherapy: insufficient stimulation of the immune response and evasion of the immune system. This provides a robust platform against invasive cancer and recurrent tumors.
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Camptotecina , Inmunoterapia , Indoles , Ratones Endogámicos BALB C , Polímeros , Triptófano , Zeolitas , Animales , Indoles/química , Indoles/farmacología , Zeolitas/química , Zeolitas/farmacología , Inmunoterapia/métodos , Triptófano/química , Triptófano/farmacología , Triptófano/análogos & derivados , Ratones , Concentración de Iones de Hidrógeno , Línea Celular Tumoral , Femenino , Polímeros/química , Polímeros/farmacología , Camptotecina/química , Camptotecina/farmacología , Nanopartículas/química , Apoptosis/efectos de los fármacos , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Humanos , Terapia Fototérmica/métodos , Imidazoles/química , Imidazoles/farmacología , Antineoplásicos/química , Antineoplásicos/farmacología , Terapia CombinadaRESUMEN
An outstanding challenge for the field of metal-organic frameworks (MOFs) is structuring to form forms with greater useability. Reactive extrusion printing (REP) is a technique for the direct formation of films from their molecular components on-demand and on-location. Here we apply REP for the first time to zeolitic imidazolate frameworks (ZIFs) and study the interplay of solvent and molarity ratio on the phase distribution between ZIF-8 and ZIF-L in reactive printed films. Our results show that REP controllably directs phase formation between ZIF-L and ZIF-8 and that REP also gives control over crystal size and that high-quality ZIF-8 films, in particular, are produced in low-dispersity interconnected nanoparticulate form. Importantly, we show that REP is responsive to established surface-functionalization techniques to control important printing parameters of line width and thickness. This work expands the repertoire of REP to the important class of ZIFs.
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Consuming leafy vegetables with excessive thiophanate-methyl (TM) residue poses serious risks to human health. To realize rapidly and sensitively detecting TM in leafy vegetables, we developed a fluorescent probe based on zeolitic imidazolate framework-8-modified carbon dots using Hami melon as the green precursor (HM-CDs@ZIF-8). Meanwhile, the mechanism of HM-CDs@ZIF-8 for detecting TM was investigated and explained. The results of the performance tests showed that the prepared HM-CDs@ZIF-8 exhibited high sensitivity, excellent selectivity, robust anti-interference capability, reliable reproducibility and repeatability, and long-term stability. After optimization experiments, the fluorescence intensity of HM-CDs@ZIF-8 showed a strong linear correlation with the concentration of TM (0.00171-3.4239 mol/L) with a detection limit of 2.025 µmol/L. The HM-CDs@ZIF-8 was successfully applied to determine TM in spiked leafy vegetables with satisfactory recoveries of 96-105%. The relative standard deviations were in the range of 0.26-2.55%. The sensor has a promising application for detecting TM in leafy vegetables.
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Carbono , Puntos Cuánticos , Tiofanato , Verduras , Verduras/química , Puntos Cuánticos/química , Carbono/química , Tiofanato/química , Tiofanato/análisis , Contaminación de Alimentos/análisis , Estructuras Metalorgánicas/química , Residuos de Plaguicidas/análisis , Residuos de Plaguicidas/química , Cucurbitaceae/química , Límite de Detección , Colorantes Fluorescentes/química , Espectrometría de Fluorescencia , Hojas de la Planta/químicaRESUMEN
Enzyme immobilization by metal organic frameworks (MOFs) is an efficient way for screening active constituents in natural products. However, the enzyme's biocatalysis activity is usually decreased due to unfavorable conformational changes during the immobilization process. In this study, sodium cholate was firstly used as the modifier for zeolitic imidazolate framework-8 (ZIF-8) immobilized lipase to increase both the stability and activity. More importantly, with the help of solubilization of sodium cholate, a total of 3 flavonoids and 6 alkaloids candidate compounds were fished out. Their structures were identified and the enzyme inhibitory activities were verified. In addition, the binding information between the candidate compound and the enzyme was displayed by molecular docking. This study provides valuable information for the improvement of immobilized enzyme activity and functional active ingredients in complicated medicinal plant extracts.
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Inhibidores Enzimáticos , Enzimas Inmovilizadas , Flavonoides , Interacciones Hidrofóbicas e Hidrofílicas , Lipasa , Estructuras Metalorgánicas , Simulación del Acoplamiento Molecular , Colato de Sodio , Solubilidad , Lipasa/antagonistas & inhibidores , Lipasa/química , Lipasa/metabolismo , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/antagonistas & inhibidores , Estructuras Metalorgánicas/química , Colato de Sodio/química , Flavonoides/química , Flavonoides/farmacología , Inhibidores Enzimáticos/farmacología , Inhibidores Enzimáticos/química , Ligandos , Alcaloides/química , Alcaloides/farmacología , Extractos Vegetales/química , Extractos Vegetales/farmacologíaRESUMEN
To realize high-quality vascularized bone regeneration, we developed a multifunctional hydrogel (SHPP-ZB) by incorporating BMP-2@ZIF-8/PEG-NH2 nanoparticles (NPs) into a sodium alginate/hydroxyapatite/polyvinyl alcohol hydrogel loaded with PDGF-BB, allowing for the sequential release of angiogenic and osteogenic growth factors (GFs) during bone repair. ZIF-8 served as a protective host for BMP-2 from degradation, ensuring high encapsulation efficiency and long-term bioactivity. The SHPP-ZB hydrogel exhibited enhanced mechanical strength and injectability, making it suitable for complex bone defects. It provided a swelling interface for tissue interlocking and the early release of Zn2+ and tannin acid (TA) to exert antioxidant and antibacterial effects, followed by the sequential release of angiogenic and osteogenic GFs to promote high-quality vascularized bone regeneration. In vitro experiments demonstrated the superior angiogenic and osteogenic properties of SHPP-ZB compared to other groups. In vivo experiments indicated that the sequential delivery of GFs via SHPP-ZB hydrogel could improve vascularized bone regeneration. Further, RNA sequencing analysis of regenerative bone tissue revealed that SHPP-ZB hydrogel promoted vascularized bone regeneration by regulating JUN, MAPK, Wnt, and calcium signaling pathways in vivo. This study presented a promising approach for efficient vascularized bone regeneration in large-scale bone defects.
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Porous ZIF-8 and ZIF-67 were synthesized via a green steam-assisted dry-gel technique and investigated as potential catalysts for CO2 electroreduction. The synthesis conditions are found to significantly influence the growth of these metal-organic frameworks (MOFs). Notably, the water content employed during synthesis plays a crucial role in shaping the morphological properties of ZIF-8. Specifically, a moderate water content results in the formation of uniform ZIF-8 with a size distribution ranging from 240 to 440 nm. During CO2 electroreduction, these morphological properties exert substantial effects on the selectivity for CO formation, thereby facilitating the production of syngas with adjustable CO: H2 ratios. This feature holds promise for the widespread adoption of syngas as a clean alternative to fossil fuels, offering potential benefits for electricity generation and liquid fuel production. Despite sharing similar structural properties with ZIF-8, ZIF-67 exhibits distinct performance characterized by its limited selectivity for CO2 electroreduction. This discrepancy is attributed to the different metal centers of the two MOFs, resulting in the distinct activation of CO2 and H2O molecules and their further reduction. This finding highlights the critical role of metal centers in MOF-based materials for electrocatalysis application.
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Metal-organic framework (MOF) derivatives with tunable pore structure and improved conductivity are intensively designed as electroactive materials. Incorporating structure directing agents (SDA) is beneficial for designing MOF derivatives with excellent electrochemical performances. Ammonium fluoroborate has been reported as an effective SDA, coupled with cobalt salt and 2-methylimidazole, to synthesize zeolitic imidazolate framework-67 (ZIF-67) derivatives for charge storage. However, the synthetic environment for growing cobalt-based active materials is relatively complex. In this study, cobalt tetrafluoroborate (Co(BF4)2) is proposed as a novel cobalt precursor, supplementing cobalt ions and acting as the SDA in a single chemical, to synthesize the cobalt-based electroactive material of energy storage electrodes. Interactions between solvent molecules and solutes play significant roles on the morphology, composition, and electrochemical performance of active materials. Deionized water, methanol and ethanol are used as precursor solvents to understand their effects on material and electrochemical properties. The optimal electrode presents a specific capacitance of 608.3 F/g at 20 mV/s, attributed to the highest electrochemical surface area and evident compositions of cobalt fluoride and hydroxide. A battery supercapacitor hybrid achieves the maximum energy density of 45 Wh/kg at 429 W/kg. The CF retention of 100% and Coulombic efficiency of 99% are achieved after 10,000 cycles.
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BACKGROUND: Aflatoxin B1 (AFB1), is a potent hepatic carcinogen which causes cancer by inducing DNA changes in the liver cells. Variety of methods have been developed for detection of AFB1 which are based on single mode detection strategy. Fabrication of novel platform which are compatible for multimodal detection of AFB1 provide robust performance for reliable detection of AFB1. In this study, we aimed to develop a robust biosensing platform that combines electrochemical and fluorescence techniques for the sensitive and specific detection of Aflatoxin B1. RESULTS: The sensing platform includes the magnetic core-shell Fe3O4@AuNPs and zeolitic imidazolate framework-8 (ZIF-8). In electrochemical mode, the applied voltametric approach was used through functionalization of glassy carbon electrode and exhibited a linear range between 0.5 and 10000 pg mL-1 with LOD of 0.32 pg mL-1. Fluorescence analysis was based on the FRET on/off status of FAM-functionalized aptamer deposited on the same platform. The FAM emission recovered by the addition of AFB1 concentration in the range of 6-60 fg mL-1 with the LOD of 0.20 fg mL-1. The real sample analysis demonstrated satisfactory relative recoveries in the range of 92.81-105.32 % and 91.66-106.66 % using the electrochemical and fluorescence methods, respectively, and its reliability was confirmed by the HPLC technique. SIGNIFICANCE: The experimental results affirm that the proposed aptasensor serves as a sensitive, efficient, and precise platform for monitoring AFB1 in both electrochemical and fluorescence detection approaches. Proposed strategy showed efficient selectivity among different analytes and was reproducible. Furthermore, the applicability of biosensor was confirmed in food and biological samples.
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Aflatoxina B1 , Técnicas Biosensibles , Técnicas Electroquímicas , Oro , Aflatoxina B1/análisis , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Oro/química , Aptámeros de Nucleótidos/química , Nanopartículas del Metal/química , Límite de Detección , Espectrometría de Fluorescencia , Estructuras Metalorgánicas/química , Fluorescencia , Zeolitas/químicaRESUMEN
The development of efficient and cost-effective electrocatalysts to overcome the intrinsic sluggish kinetics of the oxygen reduction reaction (ORR) in zinc-air batteries is crucial. In this study, we introduce a strategy that integrates a template-assisted synthesis with subsequent thermal treatment to fabricate an active and stable cobalt-based nitrogen-doped carbon electrocatalyst, denoted as Co-N-CNT. The strategy adjusts the disordered architecture of the zeolitic imidazolate framework (ZIF) through the synergistic effect of bimetallic species, restricted the growth of zeolitic imidazolate framework nanoleaves (ZIF-L) using salt templates, and directed the transformation from a two-dimensional blade-like morphology to a three-dimensional multi-tiered composite structure. Notably, the Co-N-CNT-800 sample, synthesized at an optimized pyrolysis temperature of 800 °C, exhibits a half-wave potential of 0.89 V and demonstrates stability with sustained cycling over 21 h, which is comparable to the performance of commercial Pt/C electrocatalysts. Moreover, when employed as the cathode in zinc-air batteries, Co-N-CNT-800 not only surpasses Pt/C in terms of power density but also exhibits long-term charge/discharge stability. This findings offer a viable pathway for the design of active and cost-effective ORR electrocatalysts, holding promise for applications in the electrochemical energy storage and conversion systems.
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Excessive reactive oxygen species (ROS) can lead to the imbalance of antioxidant system in the body and cause oxidative damage to cells. It is imperative to rationally design nanomaterials with high catalytic activity and multiple antioxidant activities. Here, line peppers-derived carbon dots (CDs) is encapsulated into zeolitic imidazolate framework-8 (CDs@ZIF-8) to achieve enhanced antioxidant activities for improved protective effect on cells. This nanosystem has a broad spectrum of antioxidant properties, which can effectively remove a variety of intracellular ROS and protect cells from ROS-induced death and cytoskeleton damage. In addition, CDs@ZIF-8 can reduce malondialdehyde (MDA) level and increase the enzyme activities of superoxide dismutase (SOD) and glutathione peroxidase (GPx), as well as the level of glutathione (GSH) in human kidney proximal tubular epithelial cells (HK-2) cells. Mechanism studies demonstrated that CDs@ZIF-8 can up-regulate the expression of nuclear factor erythroid 2-related factor 2 (Nrf2) and heme oxygenase-1 (HO-1), allowing the regulation of antioxidant enzymes to further achieve antioxidant effect. Besides, CDs@ZIF-8 inhibited the secretion of proinflammatory cytokines. This work demonstrates that the constructed CDs@ZIF-8 with multi-antioxidant activity can act as a highly efficient intracellular ROS scavenger and provide potential for the application in related oxidative stress-induced diseases.
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Antioxidantes , Carbono , Puntos Cuánticos , Especies Reactivas de Oxígeno , Humanos , Antioxidantes/farmacología , Antioxidantes/química , Carbono/química , Carbono/farmacología , Especies Reactivas de Oxígeno/metabolismo , Puntos Cuánticos/química , Línea Celular , Citoprotección/efectos de los fármacos , Estrés Oxidativo/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Propiedades de Superficie , Tamaño de la Partícula , Zeolitas/química , Zeolitas/farmacología , Imidazoles/química , Imidazoles/farmacología , Factor 2 Relacionado con NF-E2/metabolismoRESUMEN
Osteoarthritis treatment remains a significant clinical challenge. Quercetin, a natural flavonoid with anti-inflammatory and antiapoptotic properties, might be utilized to treat OA. However, poor water solubility and short joint retention duration limit its bioavailability and translation to clinical applications. A one-step self-assembly method was utilized to fabricate quercetin-loaded zeolitic imidazolate framework-8 (Qu@ZIF-8) nanoparticles using zinc ions, 2-methylimidazole, and quercetin. In vitro tests showed that Qu@ZIF-8 nanoparticles released pH-responsive agents into chondrocytes, effectively protecting them from interleukin (IL)-induced inflammation and apoptosis, thereby promoting cartilage anabolic activities. These underlying mechanisms revealed a remarkable increase of autophagy in IL-ß-treated chondrocytes, followed by the inhibition of the Pi3k/Akt signaling pathway, which contributed to the protective effect of Qu @ZIF-8. By the establishment of medial meniscus instability (DMM) in OA mice, Qu@ZIF-8 substantially improved cartilage structural integrity and chondrocyte status, as well as attenuated OA progression. Importantly, Qu@ZIF-8 outperformed quercetin alone in the treatment of OA due to its control release. The combined research findings indicate that Qu@ZIF-8 shields chondrocytes from inflammation and apoptosis by activating autophagy and repressing the Pi3k/Akt pathway. This investigation may provide new insights for clinically extending the therapy of OA.
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Autofagia , Condrocitos , Nanopartículas , Osteoartritis , Fosfatidilinositol 3-Quinasas , Proteínas Proto-Oncogénicas c-akt , Quercetina , Transducción de Señal , Animales , Quercetina/química , Quercetina/farmacología , Proteínas Proto-Oncogénicas c-akt/metabolismo , Fosfatidilinositol 3-Quinasas/metabolismo , Ratones , Autofagia/efectos de los fármacos , Osteoartritis/tratamiento farmacológico , Osteoartritis/patología , Osteoartritis/metabolismo , Nanopartículas/química , Transducción de Señal/efectos de los fármacos , Condrocitos/efectos de los fármacos , Condrocitos/metabolismo , Condrocitos/patología , Zeolitas/química , Zeolitas/farmacología , Imidazoles/química , Imidazoles/farmacología , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Apoptosis/efectos de los fármacos , Masculino , Ratones Endogámicos C57BLRESUMEN
Crizotinib (CRZ), one of anaplastic lymphoma kinase tyrosine kinase inhibitors (ALK-TKIs), has emerged as a frontline treatment for ALK-positive (ALK+) lung adenocarcinoma. However, the overexpression of P-glycoprotein (P-gp, a mitochondrial adenosine triphosphate (ATP)-dependent protein) in lung adenocarcinoma lesions causes multidrug resistance (MDR) and limits the efficacy of CRZ treatment. Herein, a mitochondria-targeting nanosystem, zeolitic imidazolate framework-90@indocyanine green (ZIF-90@ICG), was fabricated to intervene in mitochondria and overcome drug resistance. Due to the zinc ion (Zn2+) interference of ZIF-90 and the photodynamic therapy (PDT) of ICG, this nanosystem is well suited for damaging mitochondrial functions, thus downregulating the intracellular ATP level and inhibiting P-gp expression. In addition, systematic bioinformatics analysis revealed the upregulation of CD44 in CRZ-resistant cells. Therefore, hyaluronic acid (HA, a critical target ligand of CD44) was further modified on the surface of ZIF-90@ICG for active targeting. Overall, this ZIF-90@ICG nanosystem synergistically increased the intracellular accumulation of CRZ and reversed CRZ resistance to enhance its anticancer effect, which provides guidance for nanomedicine design to accurately target tumours and induce mitochondrial damage and represents a viable regimen for improving the prognosis of patients with ALK-TKIs resistance. STATEMENT OF SIGNIFICANCE: The original aim of our research was to combat multidrug resistance (MDR) in highly aggressive and lethal lymphoma kinase-positive (ALK+) lung adenocarcinoma. For this purpose, a cascade-targeted system was designed to overcome MDR, integrating lung adenocarcinoma-targeted hyaluronic acid (HA), mitochondrion-targeted zeolitic imidazolate framework-90 (ZIF-90), the clinically approved drug crizotinib (CRZ), and the fluorescence imaging agent/photosensitizer indocyanine green (ICG). Moreover, using a "two birds with one stone" strategy, ion interference and oxidative stress induced by ZIF-90 and photodynamic therapy (PDT), respectively, disrupt mitochondrial homeostasis, thus downregulating adenosine triphosphate (ATP) levels, inhibiting MDR-relevant P-glycoprotein (P-gp) expression and suppressing tumour metastasis. Overall, this research represents an attempt to implement the concept of MDR reversal and realize the trade-offs between MDR and therapeutic effectiveness.
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Quinasa de Linfoma Anaplásico , Crizotinib , Resistencia a Antineoplásicos , Imidazoles , Neoplasias Pulmonares , Mitocondrias , Zeolitas , Humanos , Mitocondrias/metabolismo , Mitocondrias/efectos de los fármacos , Neoplasias Pulmonares/tratamiento farmacológico , Neoplasias Pulmonares/patología , Neoplasias Pulmonares/metabolismo , Resistencia a Antineoplásicos/efectos de los fármacos , Crizotinib/farmacología , Quinasa de Linfoma Anaplásico/metabolismo , Zeolitas/química , Zeolitas/farmacología , Imidazoles/farmacología , Imidazoles/química , Animales , Línea Celular Tumoral , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Ratones , Ratones Desnudos , FotoquimioterapiaRESUMEN
Ratiometric fluorescence detection is endowed with higher accuracy than single fluorescence signal assay. In this work, we construct a ratiometric fluorescence probe for the facile quantification of sulfadimethoxine (SDM) in foods. By wrapping N-doped carbon dots (N-CDs) and gold nanoclusters (AuNCs) into zeolitic imidazolate framework-8 (ZIF-8), the nanocomposite of N-CDs/AuNCs@ZIF-8 is facilely prepared and emits two fluorescence including 475 nm from N-CDs and 650 nm from AuNCs. Since bovine serum albumin (BSA) is the stabilizer of AuNCs, SDM can form a complex with BSA, resulting in the fluorescence quenching of AuNCs at 650 nm by a static quenching mechanism. In contrast, SDM has a rare influence on the fluorescence of N-CDs (475 nm). As a result, the use of the probe of N-CDs/AuNCs@ZIF-8 for SDM detection enables simultaneous measurement of response signal and reference signal. Under the optimal condition, the SDM assay based on the probe has a good linear relationship within 10 to 2 × 106 ng/mL and the limit of detection (LOD) is low to 1.064 ng/mL. In addition, the fluorescent probe shows good reliability for the detection of SDM in practical food samples.
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The main challenge in the preparation of MOF-based mixed matrix membranes is to construct a good interface morphology to improve the gas separation performance and stability of the membranes. Herein, high-aspect-ratio ZIF-8 nanoplates for H2/CO2 separation membranes were synthesized by direct template conversion. The ZIF-8 nanoplates were prepared with the commercial Matrimid polymer to form MMMs by the flat scraping method. The homogeneous dispersion of high-aspect-ratio nanoplates in the membrane and the good compatibility between the filler and the matrix caused by the thermal annealing operation improve the gas separation performance and mechanical properties of MMMs. The H2/CO2 selectivity of MMMs loaded with 30 wt % ZIF-8 nanoplates increased to 10.3, and the H2 permeability was 330.1 Barrer. This synthesis method can be extended to prepare various ZIF nanoplates with elevated aspect ratios to obtain excellent performance fillers for gas separation of MMMs. In addition, the thermal annealing operation allows more efficient gas separation in polymer membranes and is a feasible way to design excellent and stable MMMs.
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In the paper, high specific surface area (SSA) mono and bimetallic zeolitic imidazolate frameworks (ZIFs) based on zinc and cobalt metals are successfully synthesized at room temperature using different ratios of Zn to Co salts as precursors and ammonium as a solvent to tailor the properties of the produced ZIF and optimize the efficiency of the particles in water treatment from dye and copper ions, simultaneously. The results declare that monometallic and bimetallic ZIF microparticles are formed using ammonium and the tuning of pore sizes and also increasing the SSA by inserting the Co ions in Zn-ZIF particles is accessible. It leads to a significant increase in the thermal stability of bimetallic Zn/Co-ZIF and the appearance of an absorption band in the visible region due to the existence of Co in the bimetallic structures. The bandgap energies of bimetallic ZIFs are close to that of the monometallic Co-ZIF-8, indicating controlling the bandgap by Co ZIF. Furthermore, the ZIFs samples are applied for water treatment from copper ions (10 and 184 ppm) and methylene blue (10 ppm) under visible irradiation and the optimized multifunctional bimetallic Zn/Co ZIF is introduced as an admirable candidate for water treatment even in acidic conditions.
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Upgrading biomass-derived bioethanol to higher-order alcohols using conventional biotechnological approaches is challenging. Herein, a novel, magnetic metal-organic-framework-based cofactor regeneration system was developed using ethanol dehydrogenase (EtDH:D46G), NADH oxidase (NOX), formolase (FLS:L482S), and nicotinamide adenine dinucleotide (NAD+) for converting rice straw-derived bioethanol to acetoin. A magnetic zeolitic imidazolate framework-8@Fe3O4/NAD+ (ZIF-8@Fe3O4/NAD+) regeneration system for cell-free cascade reactions was introduced and used to encapsulate EtDH:D46G, NOX, and FLS:L482S (ENF). ZIF-8@Fe3O4/NAD+ENF created an efficient microenvironment for three-step enzyme cascades. Under the optimized conditions, the yield of acetoin from 100 mM bioethanol using ZIF-8@Fe3O4/NAD+ENF was 90.4 %. The regeneration system showed 97.1 % thermostability at 50 °C. The free enzymes retained only 16.3 % residual conversion, compared with 91.2 % for ZIF-8@Fe3O4/NAD+ENF after ten cycles. The magnetic metal-organic-framework-based cofactor regeneration system is suitable for enzymatic cascade biotransformations and can be extended to other cascade systems for potential biotechnological applications.
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Acetoína , Biomasa , Etanol , Estructuras Metalorgánicas , Etanol/metabolismo , Etanol/química , Estructuras Metalorgánicas/química , Acetoína/metabolismo , NAD/metabolismo , Complejos Multienzimáticos/metabolismo , Complejos Multienzimáticos/química , Biocombustibles , Alcohol Deshidrogenasa/metabolismo , Enzimas Inmovilizadas/metabolismo , Enzimas Inmovilizadas/químicaRESUMEN
We proposed and demonstrated highly sensitive hybrid surface-enhanced Raman scattering (SERS) substrates, which are grating-integrated gold nanograsses (GIGN) that are tip-selectively encapsulated by ZIF-8 nanospheres (GIGN/tip-ZIF). This unique structure is realized through the tip-selective modification of GIGN by polyvinylpyrrolidone (PVP), and then, the tips of the GIGN were encapsulated by ZIF-8 nanospheres. The ZIF-8 nanospheres can adsorb analyte molecules, resulting in the spatial overlap between the analyte molecules and the "hotspots" on the tips of GIGN. Such a unique GIGN/tip-ZIF hybrid SERS substrate exhibits high sensitivity and quantitative detection ability. The detection limits can reach as low as 10-11 M, and the relative standard deviation is 5.59% for 4-aminothiophenol (4-ATP). In a wide range of concentrations from 10-5 to 10-11 M, the SERS intensity and concentration relationship can be fitted as a sigmoidal curve with R2 = 0.988. These indicate that the GIGN/tip-ZIF hybrid SERS substrates have broad applications in detecting toxic and harmful substances in food safety, disease diagnosis, and environmental monitoring.
RESUMEN
Evodiamine (EVO), a natural bioactive compound extracted from Evodia rutaecarpa, shows therapeutic ability against malignant melanoma. However, the poor solubility and bioavailability of EVO limit its clinical application. Metal-organic frameworks (MOFs) have shown excellent physical and chemical properties and are widely used as drug delivery systems. Among them, zeolitic imidazolate framework-8 (ZIF-8) is a research popular material because of its unique properties, such as hydrothermal stability, non-toxicity, biocompatibility, and pH sensitivity. In this study, in order to load EVO, a drug carrier that hyaluronic acid (HA) modified zeolitic imidazolate framework-8 (ZIF-8) is synthesized. This drug carrier has shown drug loading with 6.2 ± 0.6%, and the nano drugs (EVO@ZIF-8/HA) have good dispersibility. Owing to the decoration HA of EVO@ZIF-8, the potential of the nano drugs is reversed from the positive charge to the negative charge, which is beneficial to blood circulation in vivo. Furthermore, because the CD44-expressing in tumor cells is excessed, the endocytosis and accumulation of nano drugs in tumor cells are beneficial to improvement. Compared with free EVO, EVO@ZIF-8/HA has shown a significantly improved anti-tumor efficacy in vitro and in vivo. In summary, the drug carrier effectively addresses the challenges that are caused by the strong hydrophobicity and low bioavailability of EVO, thereby targeted tumor therapy of EVO can be achieved.