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Hypochlorite and ascorbic acid (AA), play an indispensable role in numerous physiological activities. Herein, a ratiometric colorimetric sensing strategy for the determination of hypochlorite and AA was developed via the catalytic oxidation and reduction of 3,3',5,5'-tetramethylbenzidine (TMB). Interestingly, in the presence of Fe3O4-MOF-5(Fe) and hypochlorite, TMB complexes in acidic environments were oxidized to blue oxidized TMB and further diazotized to produce yellow-green diazotized TMB, resulting in the hypochlorite concentration-dependent ratiometric variation for the absorbance at 652 and 450 nm (A450/A652). Moreover, the diazotized TMB was restored to colorless TMB due to the reducibility of AA, and the detection limit of hypochlorite and AA were 0.027 and 0.677 µM, respectively. The ratiometric colorimetric sensing platform offered higher sensitivity and better selectivity because of the specific hypochlorite-induced reaction and the excellent peroxidase-like activity of Fe3O4-MOF-5(Fe). The proposed novel strategy provided the guidance to develop sensors for successive detection of hypochlorite and AA in complicated samples.
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A smartphone-assisted electrochemiluminescence (ECL) strategy based on Ru(bpy)2(L)4+ as chromophores confined with metal - organic frameworks (Ru(bpy)2(L)4+@MOF-5) for the signal-amplified detection of miRNA-21 was developed. We synthesized a derivative of tris(2,2'-bipyridyl)ruthenium(II) complex (Ru(bpy)2(L)4+) with high charges, which can be loaded into the MOF-5 by strong electrostatic interaction to prevent from leakage. In addition, nucleic acid cycle amplification was used to quench the signal of Ru(bpy)2(L)4+@MOF-5 by ferrocene. This method was applied to detect the concentration of miRNA-21 ranging from 1.0 × 10-14-1.0 × 10-9 M with a low LOD of 7.2 fM. This work demonstrated the construction of a signal quenching strategy ECL biosensor for miRNA using Ru(bpy)2(L)4+@MOF-5 systems and its application in smartphone-assisted ECL detection.
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Técnicas Biosensibles , Técnicas Electroquímicas , Límite de Detección , Mediciones Luminiscentes , Estructuras Metalorgánicas , MicroARNs , Teléfono Inteligente , MicroARNs/análisis , MicroARNs/sangre , Técnicas Biosensibles/métodos , Mediciones Luminiscentes/métodos , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Estructuras Metalorgánicas/química , Humanos , Complejos de Coordinación/química , Compuestos Organometálicos/químicaRESUMEN
Metal-organic frameworks (MOFs) offered excellent catalytic activity due to their superior porosity, and high densities of catalytic sites in remarkable specific surfaces. In this research, we prepared a magnetic nanocomposite based on MOF-5 which is one of the prominent and practical structures that have been reported in many applications, and investigated the advantages of it as a catalyst. The multi-functional catalyst was prepared in five steps including (1) preparation of cobalt ferrite nanoparticles (CoFe2O4), (2) surface modification of cobalt ferrite using tetraethyl orthosilicate, (3) surface functionalization using 3-aminopropyl triethoxysilane, (4) preparation of MOF-5, (5) preparation of CoFe2O4@SiO2-NH2@MOF-5 nanocomposite. The resulting catalyst was evaluated by FTIR, FESEM, EDX, XRD, and VSM analyses. The CoFe2O4@SiO2-NH2@MOF-5 nanocomposite was applied as a catalyst for the quinazoline derivatives' synthesis. Various products were prepared with significant yields (90-98%) in short reaction times (20-60 min) without difficult work-up. In addition, the magnetic behavior of the catalyst allows it to be collected and recycled by a magnet and applied for six consecutive cycles without significantly reducing its efficiency. Quinazoline derivatives showed significant biological activities so their antioxidant activity was between 23.7% and 88.9% and their antimicrobial activity was in contradiction of E. coli, S. enterica, L. monocytogenes, S. aureus, and E. faecalis.
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Escherichia coli , Dióxido de Silicio , Staphylococcus aureus , Fenómenos MagnéticosRESUMEN
The flavin derivatives 10-methyl-isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were incorporated in two alternative metal-organic frameworks, (MOFs) MIL-53(Al) and MOF-5. We used a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders with one-dimensional (1D) pores and an in-situ approach during the synthesis of MOF-5 with its 3D channel network. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 5.2 wt% for 6F-MIA@MOF-5. For the high incorporation yields the probability to have more than one dye molecule in a pore volume is significant. As compared to the flavins in solution, the fluorescence spectrum of these flavin@MOF composites is broadened at the bathocromic side especially for MIA. Time-resolved spectroscopy showed that multi-exponential fluorescence lifetimes were needed to describe the decays. The fluorescence-weighted lifetime of flavin@MOF of 4 ± 1 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of "solid solutions" for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53 due to the formation of various J-aggregates. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photophysical properties of crystalline MIA and the flavin@MOF composites. In the solid flavins, π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores, single flavin molecules represent a major population and the computed MIA@MOF structures do not find π-stacking interactions with the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. To analyze the orientation of flavins in MOFs, we measured fluorescence anisotropy images of single flavin@MOF-5 crystals and a static ensemble flavin@MIL53 microcrystals, respectively. Based on image information, anisotropy distributions and overall curve of the time-resolved anisotropy curves combined with theoretical calculations, we can prove that all fluorescent flavins species have a defined and rather homogeneous orientation in the MOF framework. In MIL-53, the transition dipole moments of flavins are orientated along the 1D channel axis, whereas in MOF-5 we resolved an average orientation that is tilted with respect to the cubic crystal lattice. Notably, the more hydrophobic 6F-MIA exhibits a higher degree order than MIA. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation, defined orientation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.
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A novel magnetic porous carbon with a high specific surface and magnetization saturation, derived from a Zn/Co-MOF-5, was fabricated by direct carbonization of Zn/Co-MOF-5 without the need of additional carbon precursors under optimum pyrolysis temperature. The material was employed as an adsorbent for magnetic solid-phase extraction of four carbamates from water and tomato samples prior to high-performance liquid chromatography-tandem quadrupole mass spectrometry analysis. Under optimum conditions, the method displayed good linearity (r > 0.9987) within the concentration range 0.05-20 ng mL-1 for water samples and 0.1-40 ng g-1 for tomato samples. The limits of detection (S/N = 3) for the four carbamate pesticides were in the range 0.0006-0.013 ng mL-1 for water samples and 0.001-0.01 ng g-1 for tomato samples and satisfactory spiked recoveries in the range 86.1 to 109.1% were obtained with the relative standard deviation values from 2.1 to 14.0%. Graphical abstract.
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Oridonin (ORI) is a natural active ingredient with strong anticancer activity. But its clinical use is restricted due to its poor water solubility, short half-life, and low bioavailability. The aim of this study is to utilize the metal organic framework material MOF-5 to load ORI in order to improve its release characteristics and bioavailability. Herein, MOF-5 was synthesized by the solvothermal method and direct addition method, and characterized by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectrometer (FTIR), Thermogravimetric Analysis (TG), Brunauer-Emmett-Teller (BET), and Dynamic Light Scattering (DLS), respectively. MOF-5 prepared by the optimal synthesis method was selected for drug-loading and in vitro release experiments. HepG2 cells were model cells. MTT assay, 4',6-diamidino-2-phenylindole (DAPI) staining and Annexin V/PI assay were used to detect the biological safety of blank carriers and the anticancer activity of drug-loaded materials. The results showed that nano-MOF-5 prepared by the direct addition method had complete structure, uniform size and good biocompatibility, and was suitable as an ORI carrier. The drug loading of ORI@MOF-5 was 52.86% ± 0.59%. The sustained release effect was reliable, and the cumulative release rate was about 87% in 60 h. ORI@MOF-5 had significant cytotoxicity (IC50:22.99 µg/mL) and apoptosis effect on HepG2 cells. ORI@MOF-5 is hopeful to become a new anticancer sustained release preparation. MOF-5 has significant potential as a drug carrier material.
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Antineoplásicos/administración & dosificación , Antineoplásicos/química , Diterpenos de Tipo Kaurano/administración & dosificación , Diterpenos de Tipo Kaurano/química , Portadores de Fármacos/química , Estructuras Metalorgánicas , Apoptosis/efectos de los fármacos , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Sistemas de Liberación de Medicamentos , Liberación de Fármacos , Humanos , Modelos Moleculares , Conformación Molecular , Estructura Molecular , Análisis Espectral , TermogravimetríaRESUMEN
The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich-like interconnected porous carbon building (denoted as P@C-GO/MOF-5) via the vaporization-condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g-1 after 100 cycles) and excellent rate performance (502 mAh g-1 at 10 A g-1 ) can be obtained for the P@C-GO/MOF-5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability.
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Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials.
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In the present study, metal organic frameworks (MOFs) and aminated graphitic carbonaceous structure (ACS-RGO) through chemical synthesis prepared by a simple precipitation method and used for diazinon removal. Several techniques such as XRD , FESEM and FTIR were applied for identification of MOF-5 and ACS-RGO. Also, response surface methodology (RSM) was employed in this work to look at the effectiveness of diazinon adsorption. To forecast pesticide removal, we applied artificial neural network (ANN) and Box-Behnken Design (BBD) models. For the ANN model, a sensitivity analysis was also performed. The effect of independent variables like solution pH, various concentrations of diazinon, MOFs and ACS-RGO adsorbent dose and contact time were assessed to find out the optimum conditions. Based on the model prediction, the optimal condition for adsorption ACS-RGO and MOF-5 were determined to be pH 6.6 and 6.6, adsorbent dose of 0.59 and 0.906 g/L, and mixing time of 52.15 and 36.96 min respectively. These conditions resulted in 96.69% and 80.62% diazinon removal using ACS-RGO and MOF-5, respectively. Isotherm studies proved the adsorption of ACS-RGO and MOF-5 following the Langmuir isotherm model for diazinon removal. Diazinon removal followed by the pseudo-second and Pseudo-first order kinetics model provides a better fit for analyzing the kinetic data associated with pesticide adsorption for ACS-RGO and MOF-5, respectively. Based on the obtained results, the predicted values for the efficiency of diazinon removal with the ANN and BBD were similar (R2=0.98). Therefore, two models were able to predict diazinon removal by ACS-RGO and MOF-5.
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Grafito , Estructuras Metalorgánicas , Plaguicidas , Contaminantes Químicos del Agua , Diazinón , Grafito/química , Adsorción , Redes Neurales de la Computación , Contaminantes Químicos del Agua/química , CinéticaRESUMEN
In this study, a novel nanobiocomposite consisting of agar (Ag), tragacanth gum (TG), silk fibroin (SF), and MOF-5 was synthesized and extensively investigated by various analytical techniques and basic biological assays for potential biomedical applications. The performed Trypan blue dye exclusion assay indicated that the proliferation percentage of HEK293T cells was 71.19%, while the proliferation of cancer cells (K-562 and MCF-7) was significantly lower, at 10.74% and 3.33%. Furthermore, the Ag-TG hydrogel/SF/MOF-5 nanobiocomposite exhibited significant antimicrobial activity against both E. coli and S. aureus strains, with growth inhibition rates of 76.08% and 69.19% respectively. Additionally, the hemolytic index of fabricated nanobiocomposite was found approximately 19%. These findings suggest that the nanobiocomposite exhibits significant potential for application in cancer therapy and wound healing.
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Agar , Fibroínas , Hidrogeles , Nanocompuestos , Tragacanto , Fibroínas/química , Humanos , Hidrogeles/química , Agar/química , Nanocompuestos/química , Tragacanto/química , Escherichia coli/efectos de los fármacos , Escherichia coli/crecimiento & desarrollo , Staphylococcus aureus/efectos de los fármacos , Células HEK293 , Zinc/química , Proliferación Celular/efectos de los fármacos , Antibacterianos/farmacología , Antibacterianos/química , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Pruebas de Sensibilidad Microbiana , Células MCF-7 , Línea Celular TumoralRESUMEN
Metal-organic frameworks (MOFs) are known as potential pharmaceutical carriers because of their structure. Here, we evaluated the sub-acute administrations of MOF-5 on behavioral parameters, oxidative stress, and inflammation levels in rats. Thirty-two male Wistar rats received four injections of saline or MOF-5 at different doses which were 1, 10, and 50 mg/kg via caudal vein. Y-Maze and Morris-Water Maze (MWM) tests were used to explore working memory and spatial learning and memory, respectively. The antioxidant capacity and oxidative stress level of brain samples were assessed by ferric reducing antioxidant power (FRAP) and thiobarbituric acid-reacting substance (TBARS) assay, respectively. The expression levels of GFAP, IL-1ß, and TNF-α were also measured by quantitative real-time reverse-transcription PCR (qRT-PCR). Sub-acute administration of MOF-5 reduced the spatial learning and memory as well as working memory, dose-dependently. The levels of FRAP were significantly reduced in rats treated with MOF-5 at higher doses. The Malondialdehyde (MDA) levels increased at the dose of 50 mg/kg. Additionally, the expression levels of IL-1ß and TNF-α were significantly elevated in the rats' brains that were treated with MOF-5. Our findings indicate that sub-acute administration of MOF-5 induces cognitive impairment dose-dependently which might be partly mediated by increasing oxidative stress and inflammation.
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Antioxidantes , Estructuras Metalorgánicas , Ratas , Animales , Masculino , Ratas Wistar , Antioxidantes/metabolismo , Trastornos de la Memoria/tratamiento farmacológico , Factor de Necrosis Tumoral alfa/genética , Factor de Necrosis Tumoral alfa/metabolismo , Hipocampo/metabolismo , Encéfalo/metabolismo , Estrés Oxidativo , Inflamación/inducido químicamente , Inflamación/metabolismo , Aprendizaje por LaberintoRESUMEN
This work, reports the successful preparation a thin film by a simple and inexpensive process for quantification of a model analytes in the urine sample using HPLC-UV. To this end, cellulose paper was employed as a substrate for the in-situ synthesis of MOF-5, to increase the resistance of the prepared film. The prepared film can be reused 26 times with no reduction in its performance. The thin film prepared by MOF-5 modified cellulose substrate was utilized in thin film microextraction (TFME) method for the extraction and preconcentration of naproxen, aspirin, tolmetin, and celecoxib. Under optimal conditions, the linear dynamic range of the target analytes was 2-500 µg L-1 with correlation coefficients (R2) ranging from 0.9961 to 0.9990. Also, the limits of detection (LODs), the limits of quantification (LOQs) and relative standard deviation (RSD%) of the proposed method for selected analytes ranged between 0.57 and 0.77 µg L-1, 1.7 to 2.3 and 3.5 % to 6.2 %, respectively. Moreover, relative recoveries varied from of 94 % to 108 %, indicating the absence of matrices effect in the proposed method. Eventually, the TFME was successfully used for the extraction of selected analytes from urine samples.
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Antiinflamatorios no Esteroideos , Celulosa , Límite de Detección , Estructuras Metalorgánicas , Microextracción en Fase Sólida , Cromatografía Líquida de Alta Presión/métodos , Celulosa/química , Estructuras Metalorgánicas/química , Humanos , Antiinflamatorios no Esteroideos/orina , Antiinflamatorios no Esteroideos/análisis , Antiinflamatorios no Esteroideos/aislamiento & purificación , Microextracción en Fase Sólida/métodos , Reproducibilidad de los ResultadosRESUMEN
For the first time, composites of metal-organic framework MOF-5 and conjugated polymer polyaniline (PANI), (MOF-5/PANI), prepared using PANI in its conducting (emeraldine salt, ES) or nonconducting form (emeraldine base, EB) at various MOF-5 and PANI mass ratios, were evaluated as electrode materials for the electrochemical detection of cadmium (Cd2+) and lead (Pb2+) ions in aqueous solutions. Testing of individual components of composites, PANI-ES, PANI-EB, and MOF-5, was also performed for comparison. Materials are characterized by Raman spectroscopy, scanning electron microscopy (SEM) and dynamic light scattering (DLS), and their electrochemical behavior was discussed in terms of their zeta potential, structural, morphology, and textural properties. All examined composites showed high electrocatalytic activity for the oxidation of Cd and Pb to Cd2+ and Pb2+, respectively. The MOF/EB-1 composite (71.0 wt.% MOF-5) gave the highest oxidation currents during both individual and simultaneous detection of two heavy metal ions. Current densities recorded with MOF/EB-1 were also higher than those of its individual components, reflecting the synergistic effect where MOF-5 offers high surface area for two heavy metals adsorption and PANI offers a network for electron transfer during metals' subsequent oxidation. Limits of detection using MOF/EB-1 electrode for Cd2+ and Pb2+ sensing were found to be as low as 0.077 ppm and 0.033 ppm, respectively. Moreover, the well-defined and intense peaks of Cd oxidation to Cd2+ and somewhat lower peaks of Pb oxidation to Pb2+ were observed at voltammograms obtained for the Danube River as a real sample with no pretreatment, which implies that herein tested MOF-5/PANI electrodes could be used as electrochemical sensors for the detection of heavy metal ions in the real water samples.
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Industries persistently contribute to environmental pollution by releasing a multitude of harmful substances, including organic dyes, which represent a significant hazard to human health. As a result, the demand for effective adsorbents in wastewater treatment technology is steadily increasing so as to mitigate or eradicate these environmental risks. In response to this challenge, we have developed an advanced composite known as MOF-5/Cellulose aerogel, utilizing the Pampas plant as a natural material in the production of cellulose aerogel. Our investigation focused on analyzing the adsorption and flexibility characteristics of this novel composite for organic dye removal. Additionally, we conducted tests to assess the aerogel's reusability and determined that its absorption rate remained consistent, with the adsorption capacity of the MOF-5/cellulose aerogel composite only experiencing a marginal 5% reduction. Characterization of the material was conducted through XRD analysis, revealing the cubic structure of MOF aerogel particles under scanning electron microscopy. Our study unequivocally demonstrates the superior adsorption capabilities of the MOF-5/cellulose aerogel composite, particularly evident in its efficient removal of acid blue dye, as evaluated meticulously using UV-Vis spectrophotometric techniques. Notably, our findings revealed an impressive 96% absorption rate for the anionic dye under acidic pH conditions. Furthermore, the synthesized MOF-5/cellulose aerogel composite exhibited Langmuir isotherm behavior and followed pseudo-second-order kinetics during the absorption process. With its remarkable absorption efficiency, MOF-5/cellulose aerogel composites are poised to emerge as leading adsorbents for water purification and various other applications.
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A series of porous photocatalysts, Au-carbon-doped ZnO (Au/C/ZnO), were synthesized successfully via calcination using MOF-5 as template, with the matrix impregnated with Au nanorods through the seed-mediated method. The catalytic performance was investigated by the photodegradation of tetracycline hydrochloride (TC-HCl). Ninety percent of TC was degraded by Au/C/ZnO sample within 360 min under visible light, showing an efficient photocatalytic activity. The enhanced activity was mainly ascribed to the effect of oxygen vacancies produced by C doping during calcination process of MOF-5 and Au nanorods. The density functional theory (DFT) calculation shows that due to the intermediate energy level, the electron-hole pairs generated by photoelectricity transition were transitioned from valence band (VB) to the intermediate energy level, and further to the conduction band (CB) under irradiation. Thus, the separation efficiency of photogenerated carrier was improved in this process. Meanwhile, the surface plasmon resonance (SPR) and electromagnetic field effect of Au nanorods which were loaded on the C/ZnO promoted the separation efficiency of change carriers, and this process also provided more hot electrons for free radicals generation. This work provides an efficient method for the design and synthesis of noble metal- and non-metal-doped oxide photocatalysts and provides an effective photocatalytic technique for the antibiotic degradation under visible light, which possesses the huge application potential in the environmental purification.
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Óxido de Zinc , Fotólisis , Luz , Antibacterianos , Tetraciclina , CatálisisRESUMEN
Composites of carbons with metal oxides and metal sulfides have attracted a lot of interest as materials for energy conversion and storage applications. Herein, we report on novel N,O-doped carbon/ZnO/ZnS and N,O-doped carbon/ZnO composites (generally named C-(MOF-5/PANI)), synthesized by the carbonization of metal-organic framework MOF-5/polyaniline (PANI) composites. The produced C-(MOF-5/PANI)s are comprehensively characterized in terms of composition, molecular and crystalline structure, morphology, electrical conductivity, surface area, and electrochemical behavior. The composition and properties of C-(MOF-5/PANI) composites are dictated by the composition of MOF-5/PANI precursors and the form of PANI (conducting emeraldine salt (ES) or nonconducting emeraldine base). The ZnS phase is formed only with the PANI-ES form due to S-containing counter-ions. XRPD revealed that ZnO and ZnS existed as pure wurtzite crystalline phases. PANI and MOF-5 acted synergistically to produce C-(MOF-5/PANI)s with high SBET (up to 609 m2 g-1), electrical conductivity (up to 0.24 S cm-1), and specific capacitance, Cspec, (up to 238.2 F g-1 at 10 mV s-1). Values of Cspec commensurated with N content in C-(MOF-5/PANI) composites (1-10 wt.%) and overcame Cspec of carbonized individual components PANI and MOF-5. By acid etching treatment of C-(MOF-5/PANI), SBET and Cspec increased to 1148 m2 g-1 and 341 F g-1, respectively. The developed composites represent promising electrode materials for supercapacitors.
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The environmental application of the carbonized composites of the Zn-containing metal-organic framework MOF-5 and polyaniline (PANI) in its emeraldine salt and base forms (C-(MOF-5/PANI)) was investigated for the first time. Textural properties and particle size distributions revealed that composites are dominantly mesoporous and nanoscale in nature, while Raman spectroscopy revealed the ZnO phase beneath the carbon matrix. Adsorption of pesticide, dye, and metal cation on C-(MOF-5/PANI) composites in aqueous solutions was evaluated and compared with the behavior of the precursor components, carbonized MOF-5 (cMOF), and carbonized PANIs. A lower MOF-5 content in the precursor, a higher specific surface area, and the pore volume of the composites led to improved adsorption performance for acetamiprid (124 mg/g) and Methylene Blue (135 mg/g). The presence of O/N functional groups in composites is essential for the adsorption of nitrogen-rich pollutants through hydrogen bonding with an estimated monolayer capacity twice as high as that of cMOF. The proton exchange accompanying Cd2+ retention was associated with the Zn/Cd ion exchange, and the highest capacity (9.8 mg/g) was observed for the composite synthesized from the precursor with a high MOF-5 content. The multifunctionality of composites was evidenced in mixtures of pollutants where noticeably better performance for Cd2+ removal was found for the composite compared to cMOF. Competitive binding between three pollutants favored the adsorption of pesticide and dye, thereby hindering to some extent the ion exchange necessary for the removal of metal cations. The results emphasize the importance of the PANI form and MOF-5/PANI weight ratio in precursors for the development of surface, porosity, and active sites in C-(MOF-5/PANI) composites, thus guiding their environmental efficiency. The study also demonstrated that C-(MOF-5/PANI) composites retained studied pollutants much better than carbonized precursor PANIs and showed comparable or better adsorption ability than cMOF.
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Metal-organic frameworks are often used as a chemotherapeutic drug carrier due to their diverse metal sites and good acid degradation ability. Herein Co-doped Zn-MOF-5 nanoparticles with a high Co doping rate of 60% were synthesized for chemo-chemodynamic synergistic therapy of tumor. Co ions can mediate chemodynamic therapy through Fenton-like reaction and regulate the tumor microenvironment by consuming the reduced glutathione. The CoZn-MOF-5 shows high drug loading capacity with doxorubicin loading rate of 72.8%. The CoZn-MOF-5@PEG@DOX nanodrugs has a strong killing effect on 4T1 cancer cells, suggesting the chemo-chemodynamic synergistic effect on tumor therapy.
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Nanopartículas , Neoplasias , Línea Celular Tumoral , Cobalto/farmacología , Doxorrubicina/metabolismo , Doxorrubicina/farmacología , Doxorrubicina/uso terapéutico , Humanos , Neoplasias/patología , Microambiente Tumoral , Zinc/farmacologíaRESUMEN
Fast, efficient, and accurate detection of SARS-CoV-2 spike antigen is pivotal to control the spread and reduce the mortality of COVID-19. Nevertheless, the sensitivity of available nanobiosensors to detect recombinant SARS-CoV-2 spike antigen seems insufficient. As a proof-of-concept, MOF-5/CoNi2S4 is developed as a low-cost, safe, and bioactive hybrid nanostructure via the one-pot high-gravity protocol. Then, the porphyrin, H2TMP, was attached to the surface of the synthesized nanomaterial to increase the porosity for efficient detection of recombinant SARS-CoV-2 spike antigen. AFM results approved roughness in different ranges, including 0.54 to 0.74 µm and 0.78 to ≈0.80 µm, showing good physical interactions with the recombinant SARS-CoV-2 spike antigen. MTT assay was performed and compared to the conventional synthesis methods, including hydrothermal, solvothermal, and microwave-assisted methods. The synthesized nanodevices demonstrated above 88% relative cell viability after 24 h and even 48 h of treatment. Besides, the ability of the synthesized nanomaterials to detect the recombinant SARS-CoV-2 spike antigen was investigated, with a detection limit of 5 nM. The in-situ synthesized nanoplatforms exhibited low cytotoxicity, high biocompatibility, and appropriate tunability. The fabricated nanosystems seem promising for future surveys as potential platforms to be integrated into biosensors.
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Técnicas Biosensibles , COVID-19 , Estructuras Metalorgánicas , Técnicas Biosensibles/métodos , Humanos , SARS-CoV-2 , Glicoproteína de la Espiga del Coronavirus/químicaRESUMEN
A one-pot and facile method with assistance of high gravity was applied for the synthesis of inorganic two-dimensional MOF-5 embedded MXene nanostructures. The innovative inorganic MXene/MOF-5 nanostructure was applied in co-delivery of drug and gene, and to increase its bioavailability and interaction with the pCRISPR, the nanomaterial was coated with alginate and chitosan. The polymer-coated nanosystems were fully characterized, and the sustained DOX delivery and comprehensive cytotoxicity studies were conducted on the HEK-293, PC12, HepG2, and HeLa cell lines, demonstrating acceptable and excellent cell viability at both very low (0.1 µg.mL-1) and high (10 µg·mL-1) concentrations. The chitosan-coated nanocarriers showed superior relative cell viability compared to others, more than 60% on average of relative cell viability in all of the cell lines. Then, alginate-coated nanocarriers ranked at second place on the higher relative cell viability, more than 50% on average for all of the cell lines. Also, MTT results showed a complete dose-dependence, and by increasing the time of treatment from 24 to 72 h, the relative cell viability decreased by a meaningful slope; however, this decrease was optimized by coating the nanocarrier with chitosan and alginate. The nanosystems were also tagged with pCRISPR to analyze the potential application in the co-delivery of drug/gene. CLSM images of the HEK-293 and HeLa cell lines unveiled successful delivery of pCRISPR into the cells, and the enhanced green fluorescent protein (EGFP) reached up to ca. 26% for the HeLa cell line. Also, a considerable drug payload of 35.7% was achieved, which would be because of the interactions between the nanocarrier and the doxorubicin. In this unprecedented report pertaining to the synthesis of MXene assisted by a MOF and high-gravity technique, the methodology and the optimized ensuing MXene/MOF-5 nanosystems can be further developed for the co-delivery of drug/gene in animal models.