Amphiphilic Polymer Capped Perovskite Compositing with Nano Zr-MOF for Nanozyme-Involved Biomimetic Cascade Catalysis.

CsPbX3 perovskite nanocrystal (NC) is considered as an excellent optical material and is widely applied in optoelectronics. However, its poor water stability impedes its study in enzyme-like activity, and further inhibits its application in biomimetic cascade catalysis. Herein, for the first time, the oxidase-like and ascorbate oxidase-like activities of an amphiphilic polymer capped CsPbX3 are demonstrated, and its catalytic mechanism is further explored. Furthermore, an all-nanozyme cascade system (multifunctional CsPbBr3 @Zr-metal organic framework (Zr-MOF) and Prussian blue as oxidase-like and peroxidase-like nanozyme) is constructed with a portable paper-based device for realizing the dual-mode (ratiometric fluorescence and colorimetric) detection of ascorbic acid in a point-of-care (POC) fashion. This is the first report on the utilization of all-inorganic CsPbX3 perovskite NC in biomimetic cascade catalysis, which opens a new avenue for POC clinical disease diagnosis.

Diverse CsPbI3 assembly structures: the role of surface acids.

Surface ligand engineering, seed introduction and external driving forces play major roles in controlling the anisotropic growth of halide perovskites, which have been widely established in CsPbBr3 nanomaterials. However, colloidal CsPbI3 nanocrystals (NCs) have been less studied due to their low formation energy and low electronegativity. Here, by introducing different molar ratios of surface acids and amines to limit the monomer concentration of lead-iodine octahedra during nucleation, we report dumbbell-shaped CsPbI3 NCs obtained by the in situ self-assembly of nanospheres and nanorods with average sizes of 89 nm and 325 nm, respectively, which showed a high photoluminescence quantum yield of 89%. Structural and surface state analyses revealed that the strong binding of benzenesulfonic acid promoted the formation of a Pb(SO3-)x-rich surface of CsPbI3 assembly structures. Furthermore, the addition of benzenesulfonic acid increases the supersaturation threshold and the solubility of PbI2 in a high-temperature reaction system, and controls effectively the lead-iodine octahedron monomer concentration in the second nucleation stage. As a result, the as-synthesized CsPbI3-Sn NCs exhibited different assembly morphologies and high PLQYs, among which the role of sulfonate groups can be further verified by UV absorption and surface characteristics. The strategy provides a new frontier to rationally control the surface ligand-induced self-assembly structures of perovskites.

A ubiquitin-specific protease functions in regulating cell death and immune responses in rice.

Ubiquitin-specific proteases (UBPs) process deubiquitination in eukaryotic organisms and are widely involved in plant development and responses to environmental stress. However, their role in cell death and plant immunity remains largely unknown. Here, we identified a rice lesion mimic mutant (LMM) and cloned its causative gene, LMM22. Both dysfunction and overexpression of LMM22 gave rise to the hypersensitive response-like cell death, reactive oxygen species bursts, and activated defence responses. LMM22 encodes an active UBP that is localised to the endoplasmic reticulum (ER) and displays a constitutive expression pattern in rice. LMM22 interacts with SPOTTED LEAF 35 (SPL35), a coupling of ubiquitin conjugation to ER degradation domain-containing protein that is known to participate in ubiquitination and the regulation of cell death and disease response in rice. Additional analyses suggest that LMM22 can positively regulate and stabilise the abundance of SPL35 protein likely through its deubiquitination activity. These data therefore improve our understanding of the function of UBP in rice innate immune responses by demonstrating that LMM22 functions as a critical regulator of SPL35 in cell death and disease resistance.

Incorporation of perovskite nanocrystals into lanthanide metal-organic frameworks with enhanced stability for ratiometric and visual sensing of mercury in aqueous solution.

In-situ growth of CsPbBr3 nanocrystal into Eu-BTC was realized for synthesis of dual-emission CsPbBr3@Eu-BTC by a facile solvothermal method, and a novel ratiometric fluorescence sensor based on the CsPbBr3@Eu-BTC was prepared for rapid, sensitive and visual detection of Hg2+ in aqueous solution. The transmission electron microscopy (TEM), X-ray diffraction pattern (XRD), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) analysis were used to verify the successful incorporation of CsPbBr3 into the Eu-BTC. Meanwhile, the CsPbBr3@Eu-BTC nanocomposite maintained high fluorescence performance and stability in aqueous solution. After adding Hg2+, the green fluorescence of CsPbBr3 was quenched and the red fluorescence of Eu3+ remained unchanged, while the color changed from green to red obviously. The occurrence of dynamic quenching and electron transfer were verified by fluorescence lifetime, Stern-Volmer quenching constant and XPS analysis. The ratiometric fluorescence sensor shows high analytical performance for Hg2+ detection with a wide linear range of 0-1 µM and a low detection limit of 0.116 nM. In addition, it also shows high selectivity for the detection of Hg2+ and can be successfully applied to detect Hg2+ in environmental water samples. More importantly, a novel paper-based sensor based on the CsPbBr3@Eu-BTC ratiometric probe was successfully manufactured for the visual detection of Hg2+ by naked eyes. This new type of ratiometric fluorescent sensor shows great potential for applications in point-of-care diagnostics.

A Dual-emitting Two-dimensional Nickel-based Metal-organic Framework Nanosheets: Eu3+/Ag+ Functionalization Synthesis and Ratiometric Sensing in Aqueous Solution.

Using two-dimensional (2D) nickel-based metal organic framework (Ni-MOF) nanosheets as a matrix, Eu3+ and Ag+ were incorporated to synthesize Ag/Eu@Ni-MOF with double luminescence centers of Eu3+ ion (615 nm) and organic ligand (524 nm). And a ratiometric luminescence sensor is constructed based on Ag/Eu@Ni-MOF for sensitive detection of biothiols in aqueous solutions. The dual-emissive fluorescence properties can be tuned by changing the amounts of Ag+ ions doping. The results of temperature and pH effects on the fluorescence of Ag/Eu@Ni-MOF indicates that the Ag/Eu@Ni-MOF is a temperature-sensitive material and the fluorescence of Ag/Eu@Ni-MOF can keep stable over a wide pH range. Due to the binding of -SH in cysteine (Cys) and glutathione (GSH) with Ag+, the ligand luminescence was significantly inhibited by weakening the Ag + influence on the energy transfer process in the MOFs. Therefore, ratiometric fluorescent sensing of biomolecular thiols was realized based on the dual-emission Ag/Eu@Ni-MOF. More importantly, the fluorescence color change can be observed with naked eyes to realize visual detection. The ratiometric fluorescent sensor exhibits high performance for Cys and GSH detection with a wide linear range of 5-250 µM and a relatively low detection limit of 0.20 µM and 0.17 µM, respectively. Furthermore, the biothiols content in human serum was determined with satisfactory results. It proves the Ni-MOF nanosheets can be used as a stable matrix for construction luminescent MOFs for the first time, and validate the great potential of Ag/Eu@Ni-MOF as a ratiometric fluorescent probe for point-of-care testing (POCT) in disease diagnosis.

Encapsulation of Luminescent Guests to Construct Luminescent Metal-Organic Frameworks for Chemical Sensing.

Metal-organic frameworks (MOFs), which are a class of coordination polymers constructed by metal ions or clusters with organic ligands, have emerged as exciting inorganic-organic hybrid materials with the superiorities of inherent crystallinity, adjustable pore size, clear structure, and high degree of functionalization. The MOFs have attracted much attention to develop good luminescent functional materials due to their inherent luminescent centers of both inorganic and organic photonic units. Furthermore, the pores within MOFs can also be used to encapsulate a large number of luminescent guest species, which provides a broader luminescent property for MOF materials. MOFs possess the incomparable multifunctional advantages of inorganic and organic luminescent materials. A large number of luminescent MOFs (LMOFs) have been synthesized for applications in sensing, white-light-emitting diodes (LED), photocatalysis, biomedicine, etc. This paper reviews the encapsulation of various luminescent guests such as lanthanide ions, dyes, quantum dots, and luminescent complexes in metal-organic frameworks to construct luminous sensors with single- or double-emission centers, as well as the research progress of these sensors in chemical sensing. Finally, the challenges in these fields were outlined and the prospects for future development were put forward.

Novel recycle technology for recovering rare metals (Ga, In) from waste light-emitting diodes.

This work develops a novel process of recycling rare metals (Ga, In) from waste light-emitting diodes using the combination of pyrolysis, physical disaggregation methods and vacuum metallurgy separation. Firstly, the pure chips containing InGaN/GaN are adopted to study the vacuum separation behavior of rare metals, which aims to provide the theoretical foundation for recycling gallium and indium from waste light-emitting diodes. In order to extract the rare-metal-rich particles from waste light-emitting diodes, pyrolysis and physical disaggregation methods (crushing, screening, grinding and secondly screening) are studied respectively, and the operating parameters are optimized. With low boiling points and high saturation vapor pressures under vacuum, gallium and indium are separated from rare-metal-rich particles by the process of evaporation and condensation. By reference to the separating parameters of pure chips, gallium and indium in waste light-emitting diodes are recycled with the recovery efficiencies of 93.48% and 95.67% under the conditions as follows: heating temperature of 1373 K, vacuum pressure of 0.01-0.1 Pa, and holding time of 60 min. There are no secondary hazardous materials generated in the whole processes. This work provides an efficient and environmentally friendly process for recycling rare metals from waste light-emitting diodes.