RESUMEN
Metal-organic frameworks (MOFs) were promising adsorbents for removing antibiotics, but the inherent poor recyclability of MOF powders limits further application. Moreover, the dominant adsorption mechanisms and their quantitative assessment are less studied. Here, ultrahigh adsorption capacities of 821.51 and 931.87 mg g-1 for tetracycline (TC) and oxytetracycline (OTC), respectively, were realised by a novel adsorbents (biochar loaded with MIL-88B(Fe), denoted as BC@MIL-88B(Fe)), which were further immobilised in a 3D porous gelatin (GA) substrate. The obtained BCM/GA200 showed superior adsorption performance under wide pH ranges and under the interference of humic acid. Moreover, it can survive >8 cycles and even maintain high adsorption efficiency in different actual water samples. Notably, BCM/GA200 can selectively remove tetracyclines in a multivariate system containing other kinds of antibiotics and from a dynamic adsorption system. Most importantly, the results of X-ray photoelectron spectroscopy, 2D Fourier transform infrared correlation spectroscopy (2D-FTIR-COS) and density functional theory techniques revealed that (1) for TC adsorption, at pH < 4.0, the contribution of complexation was 25 %-45 %, whereas pore filling and hydrogen bonding accounted for 39 %-72 % of the total uptake. At 4.0 < pH < 10.0, the contribution of complexation increased to 60 %-82 %, whereas electrostatic attraction and π-π interaction were 4 %-13 % and 2 %-10 %, respectively. (2) For OTC adsorption, complexation was dominant at 3.0 < pH < 10.0, accounting for 55 %-86 % of the total uptake, and electrostatic attraction and π-π interactions caused 3 %-10 % and 3 %-15 %, respectively. (3) At pH > 10.0, pore filling dominated TC and OTC adsorption. Finally, the reaction sequences of the main adsorption mechanisms were also probed by 2D-FTIR-COS. This work solves the poor recyclability of MOF powders and provides a mechanistic insight into antibiotic removal by MOFs.
Asunto(s)
Estructuras Metalorgánicas , Oxitetraciclina , Contaminantes Químicos del Agua , Tetraciclinas/análisis , Agua/química , Adsorción , Contaminantes Químicos del Agua/química , Antibacterianos/análisis , Oxitetraciclina/análisis , Tetraciclina , Estructuras Metalorgánicas/química , CinéticaRESUMEN
CLIC5 encoded protein associates with actin-based cytoskeletal and is increasingly thought to play significant roles in human cancers. We use TCGA and GEO to explore CLIC5 expression differences, mutation and DNA methylation, TMB, MSI, and immune cell infiltration. We verified the mRNA expression of CLIC5 in human ovarian cancer cells by real-time PCR and detected the expression of CLIC5 as well as immune marker genes in ovarian cancer by immunohistochemistry. The pan-cancer analysis showed that CLIC5 is highly expressed in several malignant tumors. In some cancers, CLIC5 expression in tumor samples is associated with poorer overall survival. For example, patients with ovarian cancer with high expression of CLIC5 have a poor prognosis. CLIC5 mutation frequency increased in all tumor types. The CLIC5 promoter is hypomethylated in most tumors. CLIC5 was associated with tumor immunity and different immune cells of different tumor types, such as CD8 + T cells, tumor-associated fibroblasts, macrophages, etc. CLIC5 was positively correlated with various immune checkpoints, and TMB and MSI were correlated with dysregulation of CLIC5 in tumors. The expression of CLIC5 in ovarian cancer was detected by qPCR and IHC, and the results were consistent with the bioinformatics results. There were a strong positive correlation between CLIC5 expression and M2 macrophage (CD163) infiltration and a negative correlation with CD8 + T-cell infiltration. In conclusions, our first pan-cancer analysis offered a detailed grasp of the cancerogenic functions of CLIC5 in a variety of malignancies. CLIC5 participated in immunomodulation and performed a crucial function in the tumor microenvironment.
Asunto(s)
Canales de Cloruro , Neoplasias Ováricas , Femenino , Humanos , Fibroblastos Asociados al Cáncer , Linfocitos T CD8-positivos , Canales de Cloruro/genética , Proteínas de Microfilamentos , Neoplasias Ováricas/genética , Pronóstico , Microambiente TumoralRESUMEN
The selective removal of glyphosate (GP) from aqueous environments is crucial for ensuring human health and environmental sustainability. The preparation of hierarchical-pore MOFs and the reasonable regulation of the pore size are effective strategies for achieving selective removal. In this study, we applied hierarchical-pore UiO-66 analogues (HUiO-66s) synthesized by the template technique through a mild method for the removal of GP from water. The results showed that the maximum adsorption capacity of HUiO-66s was as high as 400 mg/g, which is higher than that of most reported adsorbents. Notably, HUiO-66s showed the highest adsorption rate and distribution coefficient for GP in a multivariate system containing different organophosphorus pesticides and antibiotics, exhibiting suitable selective adsorption performance for GP. Furthermore, GP adsorption onto HUiO-66-2 (prepared from 2 mL of MOF-5 template) did not affect the presence of competing anions and humic acids. Naturally occurring particles in the water body had an enhanced (i.e., Al2O3, sepiolite, and montmorillonite), reduced (i.e., illite and SiO2), or insignificant (i.e., kaolin) effect on the GP adsorption rate of HUiO-66-2. Further analysis based on the bulk adsorption results and microscopic characterisation indicated that the pore structure synergistically occurred with metal-ligand bonding, hydrogen bonding, and electrostatic interactions, which together determined the GP adsorption. Overall, the high adsorption and apparent adsorption selectivity of HUiO-66s facilitated the rapid separation and removal of GP in complex aqueous environments. Our findings provide insights into the transport and fate of MOFs and contaminants in natural aquatic systems.