Selective detection of paraquat by a cucurbit[7]uril-based fluorescent probe.

A simple fluorescent "on-off" system that can be utilized for the selective identification and determination of paraquat (PQ) is presented herein. 1H NMR spectroscopic data indicated that in aqueous solution the alkaloid palmatine can be partially encapsulated within the cucurbit[7]uril (Q[7]) cavity, whereby a stable 1 : 1 host-guest inclusion complex is formed. Other characterization techniques including mass spectrometry, UV-Vis and fluorescence spectroscopy also provided further evidence, and the host-guest inclusion complex was found to exhibit reasonable fluorescence intensity. It is noteworthy that the addition of PQ resulted in quenching the fluorescence of the host-guest inclusion complex, whereas the presence of 12 other pesticides did not significantly affect the fluorescence intensity. Given the linear relationship between the intensity of the fluorescence and the PQ concentration, the PQ concentration in aqueous solution was easily detected. Thus, a new method for identifying and determining the fluorescence quenching of PQ has been developed in this work.

A Cucurbit[8]uril-Based Supramolecular Framework Material for Reversible Iodine Capture in the Vapor Phase and Solution.

The safe and efficient management of hazardous radioactive iodine is significant for nuclear waste reprocessing and environmental industries. A novel supramolecular framework compound based on cucurbit[8]uril (Q[8]) and 4-aminopyridine (4-AP) is reported in this paper. In the single crystal structure of Q[8]-(4-AP), two 4-AP molecules interact with the outer surface of Q[8] and the two other 4-AP molecules are encapsulated into the Q[8] cavity to form the self-assembly Q[8]-(4-AP). Iodine adsorption experiments show that the as-prepared Q[8]-(4-AP) not only has a high adsorption capacity (1.74 g· g-1) for iodine vapor but also can remove the iodine in the organic solvent and the aqueous solution with the removal efficiencies of 95% and 91%, respectively. The presence of a large number of hydrogen bonds between the iodine molecule and the absorbent, as seen in the single crystal structure of iodine-loaded Q[8]-(4-AP) (I2@Q[8]-(4-AP)), is thought to be responsible for the exceptional iodine adsorption capacity of the material. In addition, the adsorption-desorption tests reveal that the self-assembly material has no significant loss of iodine capture capacity after five cycles, indicating that it has sufficient reusability.

A multifunctional supramolecular assembly based on cucurbit[7]uril: White light material and Fe(CN)63- detection.

White light emitting materials have broad application prospects in fields such as displays, lighting devices, etc., but developing such materials faces considerable challenges. In this study, 1,3,5-tris[4-(pyridine-4-butyl)phenyl]benzene derivative (BTPY) was synthesized and a supramolecular assembly with AIE properties named BTPY@Q[7] was prepared with cucurbit[7]uril (Q[7]). Furthermore, by adding rhodamine 6G (R6G) to it, and controlling its ratio with R6G, a dual-emission white light system (0.33, 0.33) was synthesized and used for white light emitting materials as well as anti-counterfeiting fields. In addition, based on the BTPY@Q[7]-R6G system, a light harvesting system in aqueous phase was constructed, with an energy transfer efficiency (ΦET) of 26.19 % and an antenna effect (AE) of 10.21. Interestingly, the supramolecular self-assembly can also be used as a fluorescent probe, specifically recognize Fe(CN)63- ions in water, with a detection limit of 2.5 × 10-8 M.

Green and Facile Synthesis of Spirocyclopentanes Through NaOH-Promoted Chemo- and Diastereo-Selective (3 + 2) Cycloaddition Reactions of Activated Cyclopropanes and Enamides.

A chemo- and diastereo-selective (3 + 2) cycloaddition reacition between Donor-Acceptor (D-A) cyclopropanes and α,ß-unsaturated enamides is developed for efficient access to spiro(cyclopentane-1,3'-indoline) derivatives. Simple, inexpensive and readily available NaOH is used as the sole catalyst for this process. A broad range of D-A cyclopropanes could be used as the C-3 synthons to react with oxindole-derived α,ß-unsaturated enamides. The structurally sophisticated spiro(cyclopentane-1,3'-indoline) derivatives bearing up to 3 adjacent chiral centers are afforded in excellent yields as single diastereomers.

NaOH-Promoted Chemoselective Cascade Cyclization of Cyclopropyl Esters with Unsaturated Imines: Access to Bioactive Cyclopenta[c]pyridine Derivatives.

A chemoselective cascade cycloaddition reaction is developed for green and efficient access to cyclopenta[c]pyridine derivatives. Simple and inexpensive NaOH is used as the sole catalyst for this process. The δ-carbon of cyclopropyl ester is activated as a nucleophilic carbon to initiate highly chemoselective cascade reactions. Cyclopenta[c]pyridines bearing various substituents are afforded in excellent yields. Preliminary studies on the bioactivities of the afforded products show promising antibacterial activities for potential applications in plant protections.

N-Heterocyclic Carbene (NHC)-Organocatalyzed Kinetic Resolutions, Dynamic Kinetic Resolutions, and Desymmetrizations.

The last couple of decades have witnessed tremendous development within N-heterocyclic carbene (NHC) organocatalysis. NHCs have been used as powerful organic catalysts in asymmetric synthesis. Although great achievements have been made in asymmetric NHC catalysis, their applications in kinetic resolution (KR), dynamic kinetic resolution (DKR), and desymmetrization processes have been relatively less developed. Moreover, limited activation modes have been involved in these processes. This review provides an overview of the NHC-organocatalyzed KR, DKR, and desymmetrization reactions in the preparation of chiral functional molecules. The aim is to highlight both the importance and elegance of these methods in the construction of challenging chiral compounds and to provide our own perspective on future development in this direction.

Carbene-catalyzed enal γ-carbon addition to α-ketophosphonates for enantioselective access to bioactive 2-pyranylphosphonates.

A carbene-catalyzed enantioselective [4+2] cycloaddition reaction between α,ß-unsaturated aldehydes and α-ketophosphonates is developed. The reaction affords chiral 2-pyranylphosphonates with excellent enantioselectivities. The optically enriched phosphonate products bear multiple functional groups, including unsaturated lactone and phosphonate moieties that often lead to unique bio-activities. Preliminary studies show that the products from our reactions exhibit anti-bacterial (X. oryzae pv. oryzae) and anti-viral (Tobacco Mosaic Virus) activities for potential use in plant protection.

A colorimetric and absorption ratiometric anion sensor based on indole & hydrazide binding units.

A colorimetric and absorption ratiometric anion sensor (L) based on indole and hydrazide binding units was designed and synthesized, and its recognition & sensing properties towards different anions were studied by naked-eye observations, UV-vis and (1)H NMR titration spectra. Sensor L could selectively recognize biologically important F(-), AcO(-) and H2PO4(-) in DMSO over other anions, along with a significant change in its color and absorption spectrum, resulting from the formation of corresponding 1:2 (L/F(-)) and 1:1 (L/AcO(-) and L/H2PO4(-)) complexes. The (1)H NMR titration experiments proved that sensor L experienced deprotonation of NH fragment and produced [HF2](-) species, whereas a stable H-bonding complex was formed in the presence of AcO(-) and H2PO4(-).