TY - JOUR
T1 - The Uptake and Assembly of Alkanes within a Porous Nanocapsule in Water
T2 - New Information about Hydrophobic Confinement
AU - Kopilevich, Sivil
AU - Gottlieb, Hugo
AU - Keinan-Adamsky, Keren
AU - Müller, Achim
AU - Weinstock, Ira A.
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/3/24
Y1 - 2016/3/24
N2 - In Nature, enzymes provide hydrophobic cavities and channels for sequestering small alkanes or long-chain alkyl groups from water. Similarly, the porous metal oxide capsule [{MoVI6O21(H2O)6}12{(MoV2O4)30(L)29(H2O)2}]41- (L=propionate ligand) features distinct domains for sequestering differently sized alkanes (as in Nature) as well as internal dimensions suitable for multi-alkane clustering. The ethyl tails of the 29 endohedrally coordinated ligands, L, form a spherical, hydrophobic "shell", while their methyl end groups generate a hydrophobic cavity with a diameter of 11Å at the center of the capsule. As such, C7 to C3 straight-chain alkanes are tightly intercalated between the ethyl tails, giving assemblies containing 90 to 110 methyl and methylene units, whereas two or three ethane molecules reside in the central cavity of the capsule, where they are free to rotate rapidly, a phenomenon never before observed for the uptake of alkanes from water by molecular cages or containers. In the porous metal oxide capsule [{MoVI6O21(H2O)6}12{(MoV2O4)30(L)29 (H2O)2}]41- (L=propionate), the ethyl tails of the endohedrally coordinated ligands form a spherical, hydrophobic shell, while their methyl end groups generate a hydrophobic cavity at the center of the capsule. Whereas C7 to C3 alkanes are tightly intercalated between the ethyl tails, two or three rapidly rotating ethane molecules reside in the central cavity.
AB - In Nature, enzymes provide hydrophobic cavities and channels for sequestering small alkanes or long-chain alkyl groups from water. Similarly, the porous metal oxide capsule [{MoVI6O21(H2O)6}12{(MoV2O4)30(L)29(H2O)2}]41- (L=propionate ligand) features distinct domains for sequestering differently sized alkanes (as in Nature) as well as internal dimensions suitable for multi-alkane clustering. The ethyl tails of the 29 endohedrally coordinated ligands, L, form a spherical, hydrophobic "shell", while their methyl end groups generate a hydrophobic cavity with a diameter of 11Å at the center of the capsule. As such, C7 to C3 straight-chain alkanes are tightly intercalated between the ethyl tails, giving assemblies containing 90 to 110 methyl and methylene units, whereas two or three ethane molecules reside in the central cavity of the capsule, where they are free to rotate rapidly, a phenomenon never before observed for the uptake of alkanes from water by molecular cages or containers. In the porous metal oxide capsule [{MoVI6O21(H2O)6}12{(MoV2O4)30(L)29 (H2O)2}]41- (L=propionate), the ethyl tails of the endohedrally coordinated ligands form a spherical, hydrophobic shell, while their methyl end groups generate a hydrophobic cavity at the center of the capsule. Whereas C7 to C3 alkanes are tightly intercalated between the ethyl tails, two or three rapidly rotating ethane molecules reside in the central cavity.
KW - alkanes
KW - confinement effect
KW - hydrophobicity
KW - molybdenum
KW - porous capsules
UR - http://www.scopus.com/inward/record.url?scp=84976215528&partnerID=8YFLogxK
U2 - 10.1002/anie.201511341
DO - 10.1002/anie.201511341
M3 - Article
AN - SCOPUS:84976215528
SN - 1433-7851
VL - 55
SP - 4476
EP - 4481
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 14
ER -