title: Structure modeling, synthesis and X-ray diffraction determination of an extra-large calixarene-based coordination cage and its application in drug delivery.
abstract: An extra-large octahedral coordination cage (CIAC-114) was designed and modeled based on Co4-p-tert-butylsulfonylcalix[4]arene (Co4-(SC4A-SO2)) subunits and 4,4',4''-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate (BBB) ligands via the isomorphic replacement approach built from an analogous cage structure with a smaller size. X-ray crystallography revealed that the crystals obtained through solvothermal synthesis exhibited the anticipated structure. Each CIAC-114 cage is assembled by six tetranuclear Co4-(SC4A-SO2) units as vertices, which bear a four-fold rotational symmetry, and eight tripodal BBB ligands as linkers, which hold a D3h symmetry. Among its analogues CIAC-114 has the largest overall peripheral diameter of 5.4 nm and an internal cavity of 2.7 nm. After treatment by supercritical CO2, a single crystal sample of CIAC-114 transformed into amorphous material with the retention of the cage skeleton, which demonstrated good adsorption properties towards a small drug molecule, ibuprofen (Ibu), evidenced by IR spectroscopy, (1)H NMR spectroscopy, N2 sorption analysis, and drug release experiments. The Ibu release experiment in phosphate buffered saline solution (pH = 7.4) revealed that CIAC-114 exhibited a slow drug release behavior.
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China. wpliao@ciac.ac.cn.
authors.forename: Shangchao
authors.initials: S
authors.lastname: Du
authors.forename: Tang-Qing
authors.initials: TQ
authors.lastname: Yu
authors.forename: Wuping
authors.initials: W
authors.lastname: Liao
authors.forename: Chunhua
authors.initials: C
authors.lastname: Hu
mesh_terms: D000894:Anti-Inflammatory Agents, Non-Steroidal / Q000737:chemistry*; D047250:Calixarenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D016503:Drug Delivery Systems; D007052:Ibuprofen / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D014961:X-Ray Diffraction / Q000379:methods*
chemical_list: D000894:Anti-Inflammatory Agents, Non-Steroidal; D008024:Ligands; D047250:Calixarenes; D007052:Ibuprofen