Surfactant-assisted self-assembly technology enables controlled assembly of porphyrin nanostructures and regulation of physical and chemical functions
The use of self-assembly technology to achieve controllable self-assembly of organic functional molecules on the supramolecular layer, and to further realize the regulation of their functions, is currently an important topic in the fields of supramolecular chemistry, nanotechnology, material science and other fields. As an important class of functional dye molecules, porphyrin compounds have become one of the most excellent building blocks in supramolecular chemistry due to their unique planar molecular skeleton characteristics and good conjugation system. At present, researchers have achieved fruitful research and accumulation in the step-by-step assembly of porphyrin molecular nanostructures. Surfactant-assisted assembly technology combines the advantages of colloidal chemistry and molecular assembly and attracts much attention. Considering that porphyrin compounds often have good solubility in non-polar or small polar solvents, their assembly in oil / water systems may provide researchers with more abundant information on the assembly of porphyrin molecules.
In recent years, with the strong support of the National Natural Science Foundation of China, the Ministry of Science and Technology and the Chinese Academy of Sciences, the Key Laboratory of Colloid, Interface and Chemical Thermodynamics Institute of Chemistry, Chinese Academy of Sciences has been devoted to the design of functional units and supramolecular assembly of interfaces. Recently, researchers have made new progress in the controlled assembly of metalloporphyrins, multi-dimensional advanced structures, and supramolecular chirality. The results were recently published in the Journal of the American Chemical Society (J. Am. Chem. Soc. 2010, 132, 9644–9652).
The study found that a chloroform solution of zinc porphyrin (ZnTPyP) was added dropwise to the aqueous solution of CTAB. By adjusting the concentration or aging time of the solution, hollow nanospheres, solid nanospheres, nanotubes, nanorods or Supramolecular nanostructures such as nanofibers. In addition, through a simple casting method, the obtained nanorods can be further assembled into a single-layer or multi-layer regular nanoarray structure with parallel arrangement features in the range of tens of microns, while other nanostructures cannot form a similar array structure . Research by circular dichroism data shows that although the surfactants and porphyrins used in the system are achiral compounds, the nanorods obtained by this method can show significant optical activity, while other structures Cannot show optically active signals.
The group ’s previous research has found that achiral amphiphilic molecules can form a supramolecular chiral thin film through the two-dimensional assembly of the gas / liquid interface, and revealed its universality (J. Am. Chem. Soc. 2003, 125 , 5051; J. Am. Chem. Soc. 2004, 126, 1322; J. Am. Chem. Soc. 2009, 131, 2756; Chem. Eur. J. 2008, 14, 1793). This study further shows that this symmetry breaking process can also occur at the liquid-liquid interface, providing a basis for understanding and revealing the origin of supramolecular chirality in supramolecular systems.
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