Thiyagarajan Muthiah, Samuelson Lynne A, Kumar Jayant, Cholli Ashok L
Center for Advanced Materials, University of Massachusetts Lowell, Lowell, Massachusetts 01854, USA.
J Am Chem Soc. 2003 Sep 24;125(38):11502-3. doi: 10.1021/ja035414h.
A novel template guided enzymatic approach has been developed to synthesize optically active conducting polyaniline (PANI) nanocomposites in the presence of H2O2 as an oxidant, using (+) and (-) 10-camphorsulfonic acid (CSA) as a dopant and chiral inductor. The formation of chiral polyaniline in the nanocomposites was confirmed by circular dichroism (CD). Interestingly, the CD spectra of nanocomposites formed either with (+) or with (-) CSA show the enzyme itself plays a critical role in controlling the stereospecificity of the polyaniline (PANI) in the nanocomposite. The enzyme used for the polymerization of aniline in the nanocomposite was horseradish peroxidase (HRP). It was shown that this enzyme prefers a specific helical conformation, regardless of whether induced chirality in the complex CSA-aniline is from (+) or (-) CSA. UV-vis spectra show that the polyaniline is in the conducting form, and transmission electron micrographs (TEM) show that the nanocomposites are dispersed nicely with particle size dimensions in the range of 20-50 nm. Electron diffraction patterns of these chiral polymer nanocomposites suggest that these nanocomposites are in both crystalline and amorphous states.
已开发出一种新型的模板导向酶促方法,以H2O2作为氧化剂,使用(+)和(-)10-樟脑磺酸(CSA)作为掺杂剂和手性诱导剂,来合成具有光学活性的导电聚苯胺(PANI)纳米复合材料。通过圆二色性(CD)证实了纳米复合材料中手性聚苯胺的形成。有趣的是,由(+)或(-)CSA形成的纳米复合材料的CD光谱表明,酶本身在控制纳米复合材料中聚苯胺(PANI)的立体特异性方面起着关键作用。用于纳米复合材料中苯胺聚合的酶是辣根过氧化物酶(HRP)。结果表明,无论复合物CSA-苯胺中的诱导手性是来自(+)还是(-)CSA,这种酶都偏好特定的螺旋构象。紫外可见光谱表明聚苯胺处于导电形式,透射电子显微镜(TEM)图像表明纳米复合材料分散良好,粒径尺寸在20-50nm范围内。这些手性聚合物纳米复合材料的电子衍射图谱表明,这些纳米复合材料同时处于结晶态和非晶态。