Wang Sibing, Zhang Chuanyong, Li Yi, Li Baozong, Yang Yonggang
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, P.R. China.
Chirality. 2015 Aug;27(8):543-50. doi: 10.1002/chir.22464. Epub 2015 May 20.
Single-handed twisted titania tubular nanoribbons were prepared through sol-gel transcription using a pair of enantiomers. Handedness was controlled by that of the template. The obtained samples were characterized using field-emission electron microscopy, transmission electron microscopy, diffuse reflectance circular dichroism (DRCD), and X-ray diffraction. The DRCD spectra indicated that the titania nanotubes exhibit optical activity. Although the tubular structure was destroyed after being calcined at 700 °C for 2.0 h, DRCD signals were still identified. However, the DRCD signals disappeared after being calcined at 1000 °C for 2.0 h. The optical activity of titania was proposed to be due to chiral defects. Previous results showed that straight titania tubes could be used as asymmetric autocatalysts, indicating that titania exhibit chirality at the angstrom level. Herein, it was found that they also exhibit DRCD signals, indicating that there are no obvious relationships between morphology at the nano level and chirality at the angstrom level. The nanotube chirality should originate from the chiral defects on the nanotube inner surface. The Fourier transform infrared spectra indicated that the chirality of the titania was transferred from the gelators through the hydrogen bonding between N-H and Ti-OH.
通过使用一对对映体的溶胶 - 凝胶转录法制备了单手扭曲的二氧化钛管状纳米带。手性由模板的手性控制。使用场发射电子显微镜、透射电子显微镜、漫反射圆二色性(DRCD)和X射线衍射对所得样品进行了表征。DRCD光谱表明二氧化钛纳米管表现出光学活性。尽管在700 °C下煅烧2.0 h后管状结构被破坏,但仍能识别出DRCD信号。然而,在1000 °C下煅烧2.0 h后DRCD信号消失。二氧化钛的光学活性被认为是由于手性缺陷。先前的结果表明直的二氧化钛管可以用作不对称自催化剂,这表明二氧化钛在埃级表现出手性。在此发现它们也表现出DRCD信号,这表明纳米级的形态与埃级的手性之间没有明显的关系。纳米管的手性应该源于纳米管内表面的手性缺陷。傅里叶变换红外光谱表明二氧化钛的手性是通过N - H和Ti - OH之间的氢键从凝胶剂转移而来的。