Phosphate
is an important anion in both the aquatic environment
and biological systems. The search for a selective and sensitive phosphate
ratiometric fluorescent probe to quantify the phosphate level in water
samples and body fluids is of great significance for the protection
of the ecological environment and human health. Here, a porphyrin-based
nano metal–organic framework (NMOF), PCN-224, was successfully
exploited as a simple but highly sensitive and selective single-component
ratiometric fluorescent probe with accurate composition and measurable
structure for the quantitative determination of phosphate, based on
the interesting double-emission fluorescence of the porphyrin ligand
itself. Compared with other zirconium-based NMOF probes for phosphate,
the reduced number of connections for ZrO clusters with the ligand
in PCN-224 obtained by a linker-elimination strategy simultaneously
provides more active recognition sites for phosphate, which effectively
improves the sensitivity of the zirconium-based NMOF probes. The detection
limit of the probe is only 54 nM. Additionally, the accuracy of the
ratiometric detection based on this probe was further proved by the
detection of phosphate in human serum and drinking water.
With graphene-like topology and designable functional moieties, single-layered covalent organic frameworks (sCOFs) have attracted enormous interest for both fundamental research and application prospects. As the growth of sCOFs involves the assembly and reaction of precursors in a spatial defined manner, it is of great importance to understand the kinetics of sCOFs formation. Although several large families of sCOFs and bulk COF materials based on different coupling reactions have been reported, the synthesis of isomeric sCOFs by exchanging the coupling reaction moieties on precursors has been barely explored. Herein, a series of isomeric sCOFs based on Schiff-base reaction is designed to understand the effect of monomer structure on the growth kinetics of sCOFs. The distinctly different local packing motifs in the mixed assemblies for the two isomeric routes closely resemble to those in the assemblies of monomers, which affect the structural evolution process for highly ordered imine-linked sCOFs. In addition, surface diffusion of monomers and the molecule-substrate interaction, which is tunable by reaction temperature, also play an important role in structural evolutions. This study highlights the important roles of monomer structure and reaction temperature in the design and synthesis of covalent bond connected functional nanoporous networks.
A pair of isomeric imine-based covalent organic frameworks with non-aromatic linkage has been fabricated at the graphite surface, which extends the structural diversity of surface covalent organic frameworks.
The genes coding for wheat ATG4 and ATG8 were cloned and their roles in autophagy were verified. Implications of ATG4/ATG8 in wheat responses to stresses were suggested by expression profiling. Autophagy-related proteins ATG4 and ATG8 are crucial for autophagy biogenesis. ATG4 processes ATG8 precursor to expose its C-terminal glycine for phosphatidyl ethanolamine (PE) lipidation. ATG8, in the form of ATG8-PE adduct, functions in the organization dynamics of autophagic membranes. Here, we report the identification of two/nine members of the ATG4/ATG8 family from common wheat (Triticum aestivum L.). Expression of each wheat ATG4/ATG8 could complement the autophagy activity of yeast atg4/atg8 mutant cells. GFP fusion proteins of ATG8s, especially of ATG8s with innate C-terminal-exposed glycines, localized to punctate autophagic membranes. Both of purified ATG4s could cleave ATG8s in vitro, but they had different activities and different preferences for ATG8 substrates. Two times of transcript accumulation, an early one and a late one, of ATG4s/ATG8s were detected in the early phases of the Pm21- and Pm3f-triggered wheat incompatible reactions to the powdery mildew causal fungus Blumeria graminis f. sp. tritici (Bgt), and fluorescence microscopy also revealed a Bgt-induced enhanced wheat autophagy level in the Pm21-triggered incompatible reaction. Only one time of Bgt-induced transcript accumulation of ATG4s/ATG8s, corresponding to but much higher than the late one in incompatible reactions, was detected in a susceptible line isogenic to the Pm21 resistance line. These results suggested positive roles of ATG4/ATG8-associated autophagy process in the early stage and possible negative roles in the late stage of wheat immunity response to Bgt. In addition, expression of wheat ATG4s/ATG8s was also found to be upregulated by abiotic stress factors and distinctively regulated by different phytohormones.
A nickel-catalyzed
enantioselective transfer hydrogenation and
deuteration of N-sulfonyl imines was developed. Excellent
α-selectivity and high deuterium content were achieved by using
inexpensive 2-propanol-d
8 as a deuterium
source. As a highlight, no deuteration of β-C–H and the
remote C–H of N-sulfonyl amines occurred,
which is hard to achieve using other imines or by hydrogen isotope
exchange with D2O. Mechanism studies indicated a stepwise
pathway through the [Ni–D] intermediate.
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