RESUMEN

Chiral metal nanoclusters have recently been attracting great attention. It is challenging to realize asymmetric catalysis via atomically precise metal nanoclusters. Herein, we report the synthesis and total structure determination of chiral clusters [Au7Ag8(dppf)3(l-/d-proline)6](BF4)2 (l-/d-Au7Ag8). Superatomic clusters l-/d-Au7Ag8 display intense and mirror-image Cotton effects in their CD spectra. Density functional theory (DFT) calculations were carried out to understand the correlation between electronic structures and the optical activity of the enantiomeric pair. Surprisingly, the incorporation of proline in a metal nanocluster can significantly promote the catalytic efficiency in asymmetric Aldol reactions. The increase of catalytic activity of Au7Ag8 in comparison with organocatalysis by proline is attributed to the cooperative effect of the metal core and prolines, showing the advantages of the integration of metal catalysis and organocatalysis in a metal nanocluster.

RESUMEN

A diversity of unprecedented chiral aza-crown ethers were synthesized straightforwardly from readily available and inexpensive aza-crown ethers. Catalyzed by a chiral phosphoric acid, desymmetrization of an array of symmetric N-arylated aza-crown ethers through tert-amino reaction proceeded efficiently under mild conditions to produce novel tetrahydroquinoline-fused aza-crown ethers in good to excellent yields with up to 96% ee. Our strategy opens a new route to functionalized chiral crown ethers.

RESUMEN

To study the effect of different cationic polyacrylamide organic dehydrating agents on sludge dewatering performance, eight commercially available cationic polyacrylamides of the same series with different properties were used. Based on the different cationic degree, they were named 9101, 9102, 9103, 9104, 9106, 9108, 9110, and 9112, respectively. Their properties were characterized by instruments and chemical analysis, and the indexes of sludge after treatment were also measured. The results showed that the properties of the eight organic dehydrants were different, among which the charge density, cationicity, viscosity, and Zeta potential had homologous trends, which all increased gradually from 9101 to 9112. The four indexes of 9112 were as high as 2.98 meq·L-1, 17.42%, 85.07 mPa·s, and 67.10 mV, respectively. The dewatering performance of sludge was improved by improving the specific resistance of filtration (SRF), floc properties, viscosity, Zeta potential, the bound water content, and the distribution of extracellular polymeric substances (EPS) after dosing organic dewatering agents. The results showed that the viscosity, charge density, cationic degree, and Zeta potential of the dewatering agents had a great influence on the sludge dewatering performance. The SRF of sludge was negatively correlated with the viscosity of the organic dewatering agent, and the correlation coefficient was as high as 0.92025, indicating that the sludge dewatering performance was improved mainly through the adsorption bridging effect of the organic dewatering agent in sludge dewatering.

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RESUMEN

We report herein a strategy to construct enantiopure inherently chiral macrocycles, ABCD-type heteracalix[4]aromatics, through a catalytic enantioselective intramolecular C-N bond forming reaction. A chiral ligand-palladium complex was found to efficiently induce the inherent chirality of molecules during the macrocyclization process with ee values up to >99%. The resulting ABCD-type heteracalix[4]aromatics displayed excellent and pH-triggered switchable electronic circular dichroism and circularly polarized luminescence properties.

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RESUMEN

Here we report an organocatalytic double Ugi reaction combining the enantioselective process and ee enhancement in a single operation to afford the chiral Ugi products with very high ee values. Both bisisocyanides and bisanilines tethered by carbonate and diester, respectively, were designed to accomplish this double multicomponent reaction that formed 10 new chemical bonds (4 C-N, 2 C-C, 2 C-O, and 2 N-H bonds). The strategy was further applied for the fast construction of an enantiomerically enriched macrocycle.