Antimony-centered pnictogen bonds at the stibine level have provided access to good catalysis in solution and outstanding ion transport and catalysis in lipid bilayer membranes.Strengthened pnictogen bonds on the stib...Antimony-centered pnictogen bonds at the stibine level have provided access to good catalysis in solution and outstanding ion transport and catalysis in lipid bilayer membranes.Strengthened pnictogen bonds on the stiborane level have increased catalytic activity in solution to an extent attractive for use in practice.Thus,the debate was whether or not transport and catalysis in lipid bilayer membranes would equally increase fromσ-acidic stibines toσ-acidic stiboranes.The response,we report,is no.Experimental support for this conclusion covers a new set ofσ-acidic catecholatostiborane catalysts with bioinspired catecholates,supramolecular structural X-ray and computational data,transfer hydrogenation catalysis in water,micelles and membranes,and,of course,ion transport across lipid bilayers.Decreasing ion transport with increasing ion binding defined the inverted region in the Goldilocks principle.Our results placedσ-acidic stibines with weaker pnictogen bonds in the well-explored Goldilocks normal region.σ-acidic stiboranes,however,with their strong pnictogen bonds,provided unprecedented access to the Goldilocks inverted region and emerged as unique tools to generalize the Goldilocks principle from transport to catalysis and from membranes to micelles.The reported methods and results should be of general interest in the design and rationalization of supramolecular function in biphasic systems.展开更多
基金supported by the University of Geneva,the National Centre of Competence in Research(NCCR)Molecular Systems Engineering,Switzerland(grant no.51NF40-205608)the Swiss National Science Foundation(NSF+3 种基金Swiss-ERC Advanced Grant TIMEUP,TMAG-2_209190Excellence Grant 200020204175)the Spain Ministry of Science,Innovation and Universities(MICIU/AEI of Spainproject PID2020-115637GB-I00 FEDER funds).
文摘Antimony-centered pnictogen bonds at the stibine level have provided access to good catalysis in solution and outstanding ion transport and catalysis in lipid bilayer membranes.Strengthened pnictogen bonds on the stiborane level have increased catalytic activity in solution to an extent attractive for use in practice.Thus,the debate was whether or not transport and catalysis in lipid bilayer membranes would equally increase fromσ-acidic stibines toσ-acidic stiboranes.The response,we report,is no.Experimental support for this conclusion covers a new set ofσ-acidic catecholatostiborane catalysts with bioinspired catecholates,supramolecular structural X-ray and computational data,transfer hydrogenation catalysis in water,micelles and membranes,and,of course,ion transport across lipid bilayers.Decreasing ion transport with increasing ion binding defined the inverted region in the Goldilocks principle.Our results placedσ-acidic stibines with weaker pnictogen bonds in the well-explored Goldilocks normal region.σ-acidic stiboranes,however,with their strong pnictogen bonds,provided unprecedented access to the Goldilocks inverted region and emerged as unique tools to generalize the Goldilocks principle from transport to catalysis and from membranes to micelles.The reported methods and results should be of general interest in the design and rationalization of supramolecular function in biphasic systems.
