Department of Chemistry, University of Massachusetts, Lowell, Massachusetts 01854, USA.
Langmuir. 2012 Sep 18;28(37):13380-6. doi: 10.1021/la302494a. Epub 2012 Aug 31.
Enzymatic synthesis of doped polypyrrole (PPy) complexes using oxidoreductases (specifically peroxidases) is very well established "green" methods for producing conducting polypyrrole. The importance of this approach is realized by the numerous potential opportunities of using PPy in biological applications. However, due to very high costs and low acid stability of these enzymes, there is need for more robust alternate biomimetic catalysts. Hematin, a hydroxyferriprotoporphyrin, has a similar iron catalytic active center like the peroxidases and has previously shown to catalyze polymerization of phenol monomers at pH 12. The insolubility of hematin due to extensive self-aggregation at low pH conditions has prevented its use in the synthesis of conjugated polymers. In this study, we have demonstrated the use of a micellar environment with sodium dodecylbenzenesulfonate (DBSA) for biomimetic synthesis of PPy. The micellar environment helps solubilize hematin, generating nanometer size reactors for the polymerization of pyrrole. The resulting PPy is characterized using UV-visible, Fourier transform infrared, and X-ray photoelectron spectroscopy and reveals the formation of an ordered PPy/DBSA complex with conductivities approaching 0.1 S/cm.
使用氧化还原酶（特别是过氧化物酶）酶促合成掺杂聚吡咯（PPy）复合物是一种非常成熟的“绿色”方法，可用于生产导电聚吡咯。这种方法的重要性体现在 PPy 在生物应用中的众多潜在机会上。然而，由于这些酶的成本非常高且耐酸性低，因此需要更稳健的替代仿生催化剂。血红素是一种羟基亚铁原卟啉，其铁催化活性中心与过氧化物酶相似，并已被证明可在 pH 值为 12 时催化苯酚单体的聚合。由于血红素在低 pH 条件下会发生广泛的自聚集，导致其不溶，因此无法用于合成共轭聚合物。在这项研究中，我们已经证明了使用十二烷基苯磺酸钠（DBSA）胶束环境进行血红素的仿生合成。胶束环境有助于血红素溶解，生成用于吡咯聚合的纳米级反应器。所得 PPy 采用紫外-可见、傅里叶变换红外和 X 射线光电子能谱进行表征，结果表明形成了具有接近 0.1 S/cm 电导率的有序 PPy/DBSA 复合物。
