Evolution of various porphyrin nanostructures via an oil/aqueous medium: controlled self-assembly, further organization, and supramolecular chirality.
Evolution of various porphyrin nanostructures via an oil/aqueous medium: controlled self-assembly, further organization, and supramolecular chirality.
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DOI：
10.1021/ja1001967
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发表时间：
2010-06
影响因子：
15
通讯作者：
Yunfeng Qiu;Penglei Chen;Minghua Liu
中科院分区：
文献类型：
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作者：
Yunfeng Qiu;Penglei Chen;Minghua Liu
我们已经证明了各种含卟啉的纳米结构可以很容易地通过表面活性剂辅助自组装（SAS）方法合成，其中使用油/水介质。将含锌5,10,15,20-四（4-吡啶基）-21H， 23h -卟啉（ZnTPyP）的氯甲烷溶液滴入十六烷基三甲基溴化铵（CTAB）水溶液中，可成功组装出多种ZnTPyP基纳米结构，包括空心纳米球、固体纳米球、纳米管、纳米棒和纳米纤维。当采用低浓度的CTAB水溶液时，根据老化时间的不同，可以产生空心纳米球或纳米管。相反，使用中等浓度的CTAB水溶液可以得到固体纳米球或纳米棒。此外，当使用高浓度的CTAB水溶液时，可以制备固体纳米球或纳米纤维。我们进一步表明，纳米棒可以在硅衬底上分层组织成大面积的规则纳米阵列，而其他纳米结构则不能。有趣的是，纳米棒显示出明显的超分子手性，尽管所采用的ZnTPyP是非手性的。根据扫描电子显微镜、高分辨率透射电子显微镜、快速傅立叶变换、能量色散x射线光谱、x射线衍射、紫外-可见光谱和圆二色光谱所获得的信息，提出了一个尝试性的解释。我们的研究表明，通过油/水介质的SAS方法是一种在可控方式下合成有机纳米结构的有效方法，并且这种纳米结构可以表现出不同的热学和组装性能。
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.