title: Evolution of various porphyrin nanostructures via an oil/aqueous medium: controlled self-assembly, further organization, and supramolecular chirality.
abstract: We have shown that various porphyrin-containing nanostructures can be easily synthesized by a surfactant-assisted self-assembly (SAS) method, where an oil/aqueous medium is employed. When a chloroform solution of zinc 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (ZnTPyP) was added dropwise into cetyltrimethylammonium bromide (CTAB) aqueous solution, diverse ZnTPyP-based nanostructures, including hollow nanospheres, solid nanospheres, nanotubes, nanorods, and nanofibers, were successfully assembled. Depending on the aging time, when a low-concentration CTAB aqueous solution was employed, hollow nanospheres or nanotubes were produced. In contrast, either solid nanospheres or nanorods were obtained by using a CTAB aqueous solution in moderate concentration. Moreover, solid nanospheres or nanofibers were produced, when a high-concentration CTAB aqueous solution was used. We have further shown that the nanorods can be hierarchically organized into a regular nanoarray on silicon substrates over a large area, while the other nanostructures cannot. Interestingly, the nanorods displayed distinct supramolecular chirality although the employed ZnTPyP is achiral. On the basis of the information obtained from scanning electron microscopy, high-resolution transmission electron microscopy, fast Fourier transformation, energy-dispersive X-ray spectroscopy, X-ray diffraction, and UV-vis and circular dichroism spectra, a tentative explanation has been proposed. Our investigation suggests that the SAS method via an oil/aqueous medium is an efficient way to synthesize organic nanostructures in a controlled manner, and that such nanostructures can show different chiroptical and assembly properties.
authors.affiliation: Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, No. 2 Zhongguancun Beiyijie, Beijing 100190, P. R. China.
authors.forename: Yunfeng
authors.initials: Y
authors.lastname: Qiu
authors.forename: Penglei
authors.initials: P
authors.lastname: Chen
authors.forename: Minghua
authors.initials: M
authors.lastname: Liu
mesh_terms: D000077286:Cetrimonium; D002593:Cetrimonium Compounds / Q000737:chemistry; D008854:Microscopy, Electron; D049329:Nanostructures; D009821:Oils / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry*; D014965:X-Rays
chemical_list: D002593:Cetrimonium Compounds; D009821:Oils; D011166:Porphyrins; D014867:Water; D000077286:Cetrimonium