RESUMEN
Hydrothermal synthesis based upon the use of Al3+ as the dopant and/or ethanol as the solvent is effective in promoting the growth of hematite into nanoplates rich in the (001) surface, which is highly active for a broad range of catalytic applications. However, the underpinning mechanism for the flattening of hematite crystals is still poorly comprehended. To close this knowledge gap, in this work, we have attempted intensive computational modelling to construct a binary phase diagram for Fe2O3-Al2O3 under typical hydrothermal conditions, as well as to quantify the surface energy of hematite crystal upon coverage with Al3+ and ethanol molecules. An innovative coupling of density functional theory calculation, cluster expansion and Monte Carlo simulations in analogy to machine learning and prediction was attempted. Upon successful validation by experimental observation, our simulation results suggest an optimum atomic dispersion of Al3+ within hematite in cases when its concentration is below 4 at% otherwise phase separation occurs, and discrete Al2O3 nano-clusters can be preferentially formed. Computations also revealed that the adsorption of ethanol molecules alone can reduce the specific surface energy of the hematite (001) surface from 1.33 to 0.31 J m-2. The segregation of Al3+ on the (001) surface can further reduce the specific surface energy to 0.18 J m-2. Consequently, the (001) surface growth is inhibited, and it becomes dominant after the disappearance of other surfaces upon their continual growth. This work provides atomistic insights into the synergistic effect between the aluminium textural promoter and the ethanol capping agent in determining the morphology of hematite nanoparticles. The established computation approach also applies to other oxide-based catalysts in controlling their surface growth and morphology, which are critical for their catalytic applications.
RESUMEN
Immune defense functions of silver carp (Hypophthalmichthys molitrix) and bighead carp (Hypophthalmichthys nobilis) have shown obvious evolutionary divergence. MiRNAs participate in the fine regulation of immune function. However, the evolutionary adaptation of miRNAs in the regulation of immune defense function is still poorly understood in silver carp and bighead carp. Here, small RNA libraries were constructed from the spleen tissue of one-year-old and three-year-old healthy silver carp and bighead carp, 424 and 422 known conserved miRNAs were respectively identified from the spleen of silver carp and bighead carp by bioinformatic analysis, which 398 were shared between the two species. These conserved miRNAs showed highly similar expression patterns between silver carp and bighead carp, but the abundance in spleen varied greatly in different species. Family analysis showed that miRNA families including mir-8, mir-7, mir-23, mir-338, mir-30, mir-27, mir-221, mir-19, mir-181, mir-17, mir-15, mir-148, mir-130, mir-10 and let-7 were the main miRNAs in the spleen of silver carp and bighead carp. 27 and 51 significant differentially expressed (SDE) miRNAs were identified from silver carp and bighead carp, respectively. Evolution analysis for the predicted target genes of SDE-miRNAs showed that ten biological processes such as blood coagulation, cell adhesion mediated by integrin and adaptive immune response were positively selected. In addition, immune genes including TLR3, NFATC3, MALT1, B2M, GILT and MHCII were positively selected only in silver carp, and they were specifically targeted by the SDE-miRNAs including miR-9-5p, miR-196a-5p, miR-375, miR-122, miR-722, miR-132-3p, miR-727-5p, miR-724, miR-19d-5p and miR-138-5p, respectively. PLA2G4 in Fc epsilon RI signaling pathway was positively selected only in bighead carp and was specifically targeted by the SDE-miRNAs including miR-222b, miR-22b-5p, miR-15c, miR-146a, miR-125c-3p, miR-221-5p, miR-2188-5p, miR-142a-3p, miR-212, miR-138-5p and miR-15b-5p. In particular, SDE-miRNAs such as miR-144-3p, miR-2188-3p, miR-731, miR-363-3p and miR-218b could simultaneously target multiple evolutionarily differentiated immune-related genes. These results indicated that in the spleen of silver carp and bighead carp, conserved miRNAs have obvious evolutionary adaptations in the regulation of immune defense function. The results of this study can provide valuable resources for further revealing themechanism of miRNA in the formation of resistance traits evolution between silver carp and bighead carp.
