Although polycrystalline metal‐organic framework (MOF) membranes offer several advantages over other nanoporous membranes, thus far they have not yielded good CO2 separation performance, crucial for energy‐efficient carbon capture. ZIF‐8, one of the most popular MOFs, has a crystallographically determined pore aperture of 0.34 nm, ideal for CO2/N2 and CO2/CH4 separation; however, its flexible lattice restricts the corresponding separation selectivities to below 5. A novel postsynthetic rapid heat treatment (RHT), implemented in a few seconds at 360 °C, which drastically improves the carbon capture performance of the ZIF‐8 membranes, is reported. Lattice stiffening is confirmed by the appearance of a temperature‐activated transport, attributed to a stronger interaction of gas molecules with the pore aperture, with activation energy increasing with the molecular size (CH4 > CO2 > H2). Unprecedented CO2/CH4, CO2/N2, and H2/CH4 selectivities exceeding 30, 30, and 175, respectively, and complete blockage of C3H6, are achieved. Spectroscopic and X‐ray diffraction studies confirm that while the coordination environment and crystallinity are unaffected, lattice distortion and strain are incorporated in the ZIF‐8 lattice, increasing the lattice stiffness. Overall, RHT treatment is a facile and versatile technique that can vastly improve the gas‐separation performance of the MOF membranes.
Azoospermia is one of the major reproductive disorders which cause male infertility in humans; however, the etiology of this disease is largely unknown. In the present study, six missense mutations of WT1 gene were detected in 529 human patients with non-obstructive azoospermia (NOA), indicating a strong association between WT1 mutation and NOA. The Wilms tumor gene, Wt1, is specifically expressed in Sertoli cells (SCs) which support spermatogenesis. To examine the functions of this gene in spermatogenesis, Wt1 was deleted in adult testis using Wt1flox and Cre-ERTM mice strains. We found that inactivation of Wt1 resulted in massive germ cell death and only SCs were present in most of the seminiferous tubules which was very similar to NOA in humans. In investigating the potential mechanism for this, histological studies revealed that the blood–testis barrier (BTB) was disrupted in Wt1 deficient testes. In vitro studies demonstrated that Wt1 was essential for cell polarity maintenance in SCs. Further studies found that the expression of cell polarity associated genes (Par6b and E-cadherin) and Wnt signaling genes (Wnt4, Wnt11) were downregulated in Wt1 deficient SCs, and that the expression of Par6b and E-cadherin was regulated by Wnt4. Our findings suggest that Wt1 is important in spermatogenesis by regulating the polarity of SCs via Wnt signaling pathway and that WT1 mutation is one of the genetic causes of NOA in humans.
Our method hinders the Ostwald ripening of polycrystalline MOF film during the solvothermal synthesis, allowing the growth of high-quality MOF films in just 8 min at room temperature.
In this study, we systematically explored the dependence of the homogeneity and sol-gel transition temperatures of various polyacrylonitrile (PAN) solutions on the solvent solubility parameters. The Cole-Cole slope was used to characterize the solution homogeneity, and we found that the PAN/dimethyl sulfoxide (DMSO) solution, which had a smaller Hansen solubility parameter distance between the solvent and PAN, showed better solution homogeneity than the PAN/dimethylformamide and PAN/dimethylacetamide solutions. Additionally, we found that both heating and cooling were able to cause the gelation of the PAN solution, although their mechanisms were totally different. The gelation caused by heating was ascribed to the nitrile-nitrile coupling of PAN chains, whereas the gelation caused by cooling was due to the solvent bridge effect. In this case, DMSO, which had the highest polarity and the strongest interactions with nitrile groups, caused the highest gelation temperature of the PAN solution during cooling. The gelation temperature of the PAN solution exhibits dependence on its solvent polarity.
The flexibility of the ZIF-8 aperture, which inhibits a molecular
cutoff of 3.4 Å, can be reduced by rapid heat treatment to obtain
CO2-selective membranes. However, the early stages of the
structural, morphological, and chemical changes responsible for the
lattice rigidification remain elusive. Herein, using ex situ and in situ experiments, we determine that a small
shrinkage of the unit-cell parameter, ∼0.2%, is mainly responsible
for this transformation. Systematic gas permeation studies show that
one needs to achieve this shrinkage without a disproportionately large
shrinkage in the grain size of the polycrystalline film to avoid the
formation of cracks. We show that this condition is uniquely achieved
in a short time by exposure of ZIF-8 to a mildly humid environment
where lattice parameter shrinkage is accelerated by the incorporation
of linker vacancy defects, while the shrinkage in grain size is limited.
The water-vapor-led incorporation of linker vacancy defects takes
place with an energy barrier of 123 kJ mol–1, much
higher than that for the thermal degradation of ZIF-8, <80 kJ mol–1. The latter is promoted by heat treatment in a dry
environment at a relatively higher temperature; however, this condition
does not shrink the lattice parameters at short exposure time.
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