Chiral molecules are widely prevalent in nature and biological systems, and artificial chiral nanoparticles have drawn enormous interest owing to their unique optical and physical properties. However, nanoparticles with chiral morphologies and their potential role in biology have been rarely explored. Herein, we report a seed-mediated synthesis of enantiomorphic Au nanooctopods (NOPs) and their chiralmorphology dependence of cellular uptake. With a high yield (∼80%), the chiral NOPs possess eight uniform arms that bend from 〈111〉 to 〈100〉 directions, like a propeller structure. The chiral NOPs synthesized with L-or D-glutathione (GSH) have opposite handedness, resulting in opposite circular dichroism signals, which is consistent with finite-difference time-domain simulations. D-GSH NOPs demonstrate greater than 30% (ca. 15%) enhanced cellular uptake in GL261 and bEnd.3 cells compared with L-GSH NOPs (racemic NOPs). Moreover, D-GSH NOPs modified with poly(ethylene glycol) or L-GSH are also preferred by the cells, proving the chiral-morphology dependence of cellular uptake. Our study develops the exploration of the chiral-specific interaction in biological systems, providing potential applications for drug delivery, biosensing, and tumor detection.

An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom‐economic fashion. The protocol relies on tandem cyclization of N‐cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C−C bonds, two C−X bonds (N−S and S−C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N‐sulfonylimines from readily accessible materials.

[reaction: see text] A novel methodology was developed for the efficient synthesis of 4-chloro-pyrimido[4,5-b][1,4]benzodiazepines. The key is the intramolecular Friedel-Crafts cyclization of 5-amino-4-(N-substituted)anilino-6-chloropyrimidine with either a carboxylic acid or its derivatives to construct the 4-chloro-pyrimido[4,5-b][1,4]benzodiazepine core. Subsequent nucleophilic substitution allows the introduction of one more diversity point in the target molecules. This strategy provides an efficient method to access a library of compounds based on privileged substructures that are of great interest in drug discovery.

A library of tetra-substituted purine analogues was readily prepared via parallel synthesis. This strategy relies on a key cyclization of a 4,5-diaminopyrimidine with either a carboxylic acid or its derivative to construct the 2,8,9-trisubstituted 6-chloropurine core. Further elaborations of this core allow the introduction of other diversity points. This methodology is demonstrated through the preparation of a 135-membered library of tetra-substituted purines in good yields and high purity.

Cross-linking mass spectrometry (XL-MS) has made significant progress in understanding the structure of protein and elucidating architectures of larger protein complexes. Current XL-MS applications are limited to targeting lysine, glutamic acid, aspartic acid, and cysteine residues. There remains a need for the development of novel cross-linkers enabling selective targeting of other amino acid residues in proteins. Here, a novel simple crosslinker, namely, [4,4′-(disulfanediylbis(ethane-2,1-diyl)) bis(1,2,4triazolidine-3,5-dione)] (DBB), has been designed, synthesized, and characterized. This cross-linker can react selectively with tyrosine residues in protein through the electrochemical click reaction. The DBB cross-links produced the characteristic peptides before and after electrochemical reduction, thus permitting the simplified data analysis and accurate identification for the crosslinked products. This is the first time a cross-linker is developed for targeting tyrosine residues on protein without using photoirradiation or a metal catalyst. This strategy might potentially be used as a complementary tool for XL-MS to probe protein 3D structures, protein complexes, and protein−protein interaction.

A series of (Z)-3-(naphthalen-1-yl)-2-phenylacrylonitrile derivatives have been synthesized via Knoevenagel condensation reaction. The photoisomerization takes place in the molecular crystals, which triggers the crystals to bend backward from the light...

Bifunctional asymmetric phase-transfer catalysts bearing multiple hydrogen-bonding donors have rarely been explored. The first quaternary ammonium type of these catalysts derived from cinchona alkaloids were readily prepared and found to be highly efficient catalysts for asymmetric nitro-Mannich reactions of amidosulfones. Compared with previous reports, very broad substrate generality was observed, and both enantiomers of the products were achieved in high enantio- and diastereoselectivity (90-99% ee, 13:1 to 99:1 dr).

A novel bifunctional phase-transfer catalyst 1i was found to be highly efficient for the nitro-Mannich reaction of unactivated ketone-derived imines with the introduction of the protecting group 6-methyl-2-pyridylsulfonyl to the ketimines. Density functional theory (DFT) calculations are also performed to give the possible transition-state model.