Metal-Organic Cage Receptors for Encapsulation and Sensing of Bile Acids.

Developing synthetic supramolecular receptors to solubilize, scavenge, recognize, encapsulate, and sense steroids is challenging. Despite a limited number of receptors having affinity with steroids, none exists to bind steroidal bile acids selectively. Herein, we report a C2-symmetric metal-organic cage [Pd6L24]12+ and an expanded version of the Fujita cage [Pd6L14]12+, built with a conformationally flexible ligand L2, accessed through coordination-driven self-assembly. We examined both cages for steroid recognition in water: both have certain shared characteristics and distinctive features. [Pd6L14]12+ binds hydrophobic bile acids and other steroids by forming a 1:1 complex. In contrast, the expanded [Pd6L24]12+ cage exhibits an affinity for amphiphilic bile acids and selective steroids to encapsulate them as dimers, promoted by cooperative interguest hydrogen bonding. [Pd6L24]12+ has a 5 times stronger solubility enhancement ability for cholic acid compared to [Pd6L14]12+. Further, the expanded [Pd6L24]12+ cage can selectively sense bile acids in nanomolar detection limits through indicator displacement assay by employing sulforhodamine 101 (SR101).

Water-SDS-[BMIm]Br composite system for one-pot multicomponent synthesis of pyrano[2,3-c]pyrazole derivatives and their structural assessment by NMR, X-ray, and DFT studies.

Here, we report a simple, efficient, and green protocol for the one-pot synthesis of pyrano[2,3-c]pyrazole derivatives via a sequential three-component strategy using aromatic aldehydes, malononitrile and pyrazolin-5-one in a water-SDS-ionic liquid system. This is a base and volatile organic solvent-free approach that could be applicable to a wide substrate scope. The key advantages of the method over other established protocols are very high yield, eco-friendly conditions, chromatography-free purification and recyclability of the reaction medium. Our study revealed that the N-substituent present in pyrazolinone controls the selectivity of the process. N-unsubstituted pyrazolinone favours the formation of 2,4-dihydro pyrano[2,3-c]pyrazoles whereas under identical conditions N-phenyl substituent pyrazolinone favours the formation 1,4-dihydro pyrano[2,3-c]pyrazoles. Structures of the synthesized products were established by NMR and X-ray diffraction techniques. Energy optimized structures and energy gaps between the HOMO-LUMO of some selected compounds were estimated using density functional theory to explain the extra stability of the 2,4-dihydro pyrano[2,3-c]pyrazoles over 1,4-dihydro pyrano[2,3-c]pyrazoles.

Chiral Self-Sorting in Pd6 L12 Metal-Organic Cages.

Chiral self-sorting during the formation of cage-like molecules continues to fascinate and advance our understanding of the phenomenon in general. Herein, we report the chiral self-sorting in the Pd6 L12 -type metal-organic cages. When a racemic mixture of axially chiral bis-pyridyl ligands undergo coordination-driven self-assembly with Pd(II) ions to form Pd6 L12 -type cages, the system has the option of chiral self-sorting to afford any of at least 70 pairs of (one homochiral and 69 heterochiral) enantiomers and 5 meso isomers or a statistical mixture of everything. However, the system resulted in diastereoselective self-assembly through a high-fidelity chiral social self-sorting to form a racemic mixture of D3 symmetric heterochiral [Pd6 (L6R/6S )12 ]12+ /[Pd6 (L6S/6R )12 ]12+ cages.