A built-in self-calibrating luminescence sensor based on RhB@Zr-MOF for detection of cations, nitro explosives and pesticides.

A RhB@Zr-MOF composite with dual-emission properties was successfully constructed, which comprises a zirconium-based metal-organic framework and the luminescent dye molecule, Rhodamine B (RhB), embedded via the encapsulation method. The fluorescence intensity ratio of the two emissions was found to be ca. 370 nm/590 nm for RhB@Zr-MOF. The fluorescence intensity values of the two emissions of RhB@Zr-MOF can also be affected by the structures of analytes containing different organic groups. Due to the existence of the dual-emission properties in RhB@Zr-MOF, the relative fluorescence intensity of the emission peaks was introduced as a detection index instead of absolute fluorescence intensity. RhB@Zr-MOF, which possesses the characteristics of a built-in self-calibrating fluorescence sensor, was investigated for detecting cations, nitroaromatics and pesticides. Aside from high sensitivity and selectivity, recyclability is the most important property for sensing pesticides. This work shows that RhB@Zr-MOF can maintain its stability after 5 cycles of detecting nitenpyram, with LOD of 0.2 µM. These results demonstrate that dye@MOFs with dual-emission properties can be employed as multifunctional fluorescence sensors for different types of analytes, and that RhB@Zr-MOF provides a new paradigm for analyte sensing.

Two luminescent dye@MOFs systems as dual-emitting platforms for efficient pesticides detection.

Pesticides, which can accumulate in soil, water, animals and plants, are essential to world agriculture. Developing a method that can efficiently and quickly detect toxic pesticides is of importance but still a challenge. Here, two luminescent dye@MOFs systems, Rho B@1 and Rho 6G@1, were successfully fabricated based on [Cd2(tib)(btb)(H2O)2]∙NO3∙2DMF (1). This work is the first use of two fluorescent sensors as dual-emitting platforms for detecting pesticides. As a result, the fluorescence intensity ratios between the two main emissions can be tuned using the concentrations of the dye solutions, and the emissions are at 370 nm/606 nm and 370 nm/590 nm for Rho B@1 and Rho 6G@1, respectively. The intensities of the two main emissions of Rho B@1 and Rho 6G@1 are also influenced by the chemical structures of pesticides with electron-withdrawing groups. It is important that high sensitivity and selectivity for sensing pesticides must have good recyclability. Rho B@1 and Rho 6G@1 can still remain stable regarding the detection of nitenpyram even after 5 cycles, with LODs of 0.48 nM for Rho B@1 and 3 nM for Rho 6G@1, which indicate that these two luminescent dye@MOFs systems are excellent fluorescence probe candidates for the selective detection of pesticides.

Cobalt-Catalyzed Annulation of Amides with Isocyanides via C(sp2)-H Activation.

A cobalt-catalyzed [4 + 1] cycloaddition of easily accessible amides with isocyanides for the efficient synthesis of 3-iminoisoindolinone derivatives in high yield under mild conditions via intramolecular C(sp2)-H activation and isocyanide insertion is reported. The annulation was found to be applicable to a broad range of substrates, including arylamides, heteroarylamides, and acrylamide derivatives. Strongly coordinating N-heterocyclic directing groups such as pyridine, pyrimidine, and even pyrazole were fully tolerated in this cobalt-catalyzed C-H activation reaction.

Pd-Catalyzed Intramolecular Heck Reaction, C(sp(2))-H Activation, 1,4-Pd Migration, and Aminopalladation: Chemoselective Synthesis of Dihydroindeno[1,2,3-kl]acridines and 3-Arylindoles.

Palladium-catalyzed intramolecular Heck reaction and aminopalladation of N-(2-(1-phenylvinyl)phenyl)aniline for the efficient synthesis of dihydroindeno[1,2,3-kl]acridines and 3-arylindoles via tuning of the phosphine ligands and solvents under two optimized conditions are reported. The reaction follows a 1,4-Pd migration, aminopalladation, C(sp(2))-H activation, as well as five- and six-membered-ring fusion to form different products. The dihydroindeno[1,2,3-kl]acridine derivatives showed higher triplet energy (ET) levels than common blue phosphorescent dopant and may serve as good host candidates for blue triplet emitters.

Sulfuration of the C(sp(2))-H bond of enaminones: a protocol for the synthesis of thioether using elemental sulfur as a sulfurating reagent.

Sulfuration reaction of the C(sp(2))-H bond of enaminones with elemental sulfur in the presence of CuBr/K3PO4 was carried out. It provided an efficient method for the synthesis of thioethers in moderate to good yields. The protocol was also applicable to synthesize selenides when selenium powder was used instead of sulfur powder.