Miodek Anna, Mejri-Omrani Nawel, Khoder Rabih, Korri-Youssoufi Hafsa
CNRS UMR-8182, Institut de Chimie Moléculaire et de Matériaux d'Orsay, Equipe de Chimie Bioorganique et Bioinorganique, Université Paris-Sud, Bâtiment 420, 91405 Orsay, France.
CNRS UMR-8182, Institut de Chimie Moléculaire et de Matériaux d'Orsay, Equipe de Chimie Bioorganique et Bioinorganique, Université Paris-Sud, Bâtiment 420, 91405 Orsay, France.
Talanta. 2016 Jul 1;154:446-54. doi: 10.1016/j.talanta.2016.03.076. Epub 2016 Mar 25.
Electrochemical patterning method has been developed to fabricate composite based on polypyrrole (PPy) film and poly(amidoamine) dendrimers of fourth generation (PAMAM G4). PPy layer was generated using electrochemical polymerization of pyrrole on a gold electrode. PPy film was then modified with PAMAM G4 using amines electro-oxidation method. Covalent bonding of PAMAM G4 and the formation of PPy-PAMAM composite was characterized using Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Ferrocenyl groups were then attached to such surface as a redox marker. Electrochemical properties of the modified nanomaterial (PPy-PAMAM-Fc) were studied using both amperometric and impedimetric methods to demonstrate the efficiency of electron transfer through the modified PPy layer. The obtained electrical and electrochemical properties were compared to a composite where PPy bearing carboxylic acid functions was chemically modified with PAMAM G4 by covalent attachment through formation of amid bond (PPy-CONH-PAMAM). The above mentioned studies showed that electrochemical patterning does not disturb the electronic properties of PPy. The effect of the number of functional groups introduced by the electrochemical patterning was demonstrated through the association of various compounds (ethylenediamine, PAMAM G2 and PAMAM G6). We demonstrated that such compounds could be applied in the biosensors technology. The modified PPy-PAMAM-Fc was evaluated as a platform for DNA sensing. High performance in the DNA detection by variation of the electrochemical signal of ferrocene was obtained with detection limit of 0.4 fM. Furthermore, such approach of electrochemical patterning by oxidation of amines could be applied for chemical modification of PPy and open a new way in various biosensing application involving functionalized PPy.
已经开发出一种电化学图案化方法，用于制备基于聚吡咯（PPy）薄膜和第四代聚（酰胺胺）树枝状大分子（PAMAM G4）的复合材料。通过在金电极上进行吡咯的电化学聚合来生成PPy层。然后使用胺电氧化法用PAMAM G4对PPy薄膜进行修饰。使用傅里叶变换红外光谱（FT-IR）和X射线光电子能谱（XPS）对PAMAM G4的共价键合以及PPy-PAMAM复合材料的形成进行了表征。然后将二茂铁基团作为氧化还原标记物连接到该表面。使用安培法和阻抗法研究了改性纳米材料（PPy-PAMAM-Fc）的电化学性质，以证明电子通过改性PPy层转移的效率。将所获得的电学和电化学性质与通过形成酰胺键（PPy-CONH-PAMAM）通过共价连接用PAMAM G4对带有羧酸官能团的PPy进行化学改性的复合材料进行了比较。上述研究表明，电化学图案化不会干扰PPy的电子性质。通过各种化合物（乙二胺、PAMAM G2和PAMAM G6）的缔合，证明了电化学图案化引入的官能团数量的影响。我们证明了这些化合物可应用于生物传感器技术。对改性的PPy-PAMAM-Fc作为DNA传感平台进行了评估。通过二茂铁电化学信号的变化在DNA检测中获得了高性能，检测限为0.4 fM。此外，这种通过胺氧化进行电化学图案化的方法可用于PPy的化学改性，并为涉及功能化PPy的各种生物传感应用开辟了一条新途径。
