Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram-695019, Kerala, India.
J Phys Chem B. 2009 Aug 27;113(34):11614-24. doi: 10.1021/jp9043418.
We report a soft template approach based on a custom-designed novel surfactant-cum-dopant for size and shape tuning of polyaniline nanomaterials such as nanofibers and nanotapes via emulsion and dispersion polymerization routes. A new amphiphilic 4-(3-dodecyl-8-enylphenyloxy) butane sulfonic acid was synthesized by ring-opening of butanesultone with renewable resource cardanol. The new amphiphilic dopant forms spherical micelles in water and its critical micelle concentration was determined by dye encapsulation and surface tension methods. In the emulsion route, the amphiphilic dopant complexed with aniline to produce cylindrical micellar aggregates that template exclusively for polyaniline nanofibers. The dispersion of aniline+dopant in water/toluene solvent mixture produces vesicles that selectively template for polyaniline nanotapes. The mechanism of the polyaniline nanomaterials formation was investigated by dynamic light scattering (DLS) and high-resolution transmission electron microscopy (HR-TEM). DLS of the polymerization templates in water proved the presence of micrometer range aggregates, and TEM images confirmed the shape of the cylindrical and vesicular templates. The polyaniline nanomaterials were found soluble in water and polar organic solvents for structural characterization and composition analysis by 1H NMR spectroscopy. Absorbance spectra of the nanomaterials showed free carrier tail above 900 nm in the near IR region for the delocalization of electrons in the polaron band corresponding to expanded conformation of polyaniline chains. Wide angle X-ray diffraction showed two new peaks at low angle region with d-spacing of 26.5 and 13.6 A corresponding to lamellar ordering of polyaniline chains followed by interdigitations of the amphiphilic dopant in the nanomaterials.
我们报告了一种基于定制设计的新型表面活性剂-掺杂剂的软模板方法,用于通过乳液和分散聚合路线调整聚苯胺纳米材料(如纳米纤维和纳米带)的尺寸和形状。通过丁烷砜与可再生资源腰果酚开环合成了一种新的两亲性 4-(3-十二烷基-8-烯基苯氧基)丁烷磺酸。新的两亲性掺杂剂在水中形成球形胶束,其临界胶束浓度通过染料包封和表面张力法确定。在乳液路线中,两亲性掺杂剂与苯胺复合生成圆柱形胶束聚集体,专门为聚苯胺纳米纤维模板。苯胺+掺杂剂在水/甲苯溶剂混合物中的分散体产生选择性为聚苯胺纳米带模板的囊泡。通过动态光散射(DLS)和高分辨率透射电子显微镜(HR-TEM)研究了聚苯胺纳米材料的形成机制。水相中的聚合模板 DLS 证明了存在微米级聚集体,TEM 图像证实了圆柱形和囊泡模板的形状。聚苯胺纳米材料在水中和极性有机溶剂中均具有可溶性,可通过 1H NMR 光谱进行结构表征和组成分析。纳米材料的吸收光谱在近红外区域(900nm 以上)显示出自由载流子尾部,表明电子在对应于聚苯胺链扩展构象的极化子带中离域。广角 X 射线衍射在低角度区域显示出两个新峰,其层间距为 26.5 和 13.6A,对应于聚苯胺链的层状有序排列,随后是纳米材料中两亲性掺杂剂的互穿插。