Siqueira José R, Gasparotto Luiz H S, Crespilho Frank N, Carvalho Antonio J F, Zucolotto Valtencir, Oliveira Osvaldo N
Universidade de São Paulo, IFSC, CP 369, São Carlos, SP, 13560-970, Brazil.
J Phys Chem B. 2006 Nov 16;110(45):22690-4. doi: 10.1021/jp0649089.
Electroactive nanostructured films of chitosan (Ch) and tetrasulfonated metallophthalocyanines containing nickel (NiTsPc), copper (CuTsPc), and iron (FeTsPc) were produced via the electrostatic layer-by-layer (LbL) technique. The multilayer formation was monitored with UV-vis spectroscopy by measuring the increase of the Q-band absorption from metallophthalocyanines. Results from transmission and reflection infrared spectroscopy suggested specific interactions between SO(3)(-) groups from metallophthalocyanines and NH(3)(+) from chitosan. The electroactive multilayered films assembled onto an ITO electrode were characterized by cyclic voltammetry, with Ch/NiTsPc films showing higher stability and well-defined voltammograms displaying reversible redox peaks at 0.80 and 0.75 V. These films could be used to detect dopamine (DA) in the concentration range from 5.0 x 10(-6) to 1.5 x 10(-4) mol L(-1). Also, ITO-(Ch/NiTsPc)(n)() electrodes showed higher electrocatalytic activity for DA oxidation when compared with a bare ITO electrode. On the other hand, only the Ch/FeTsPc and Ch/CuTsPc modified electrodes could distinguish between DA and ascorbic acid. These results demonstrate that versatile electrodes can be prepared by incorporation of different metallophthalocyanine molecules in LbL films, which may be used in bioanalytical applications.
通过静电逐层(LbL)技术制备了壳聚糖(Ch)与含镍(NiTsPc)、铜(CuTsPc)和铁(FeTsPc)的四磺化金属酞菁的电活性纳米结构薄膜。通过紫外可见光谱法测量金属酞菁Q带吸收的增加来监测多层膜的形成。透射和反射红外光谱结果表明,金属酞菁的SO(3)(-)基团与壳聚糖的NH(3)(+)之间存在特定相互作用。通过循环伏安法对组装在ITO电极上的电活性多层膜进行了表征,Ch/NiTsPc膜显示出更高的稳定性,明确的伏安图在0.80和0.75 V处显示出可逆的氧化还原峰。这些薄膜可用于检测浓度范围为5.0×10(-6)至1.5×10(-4) mol L(-1)的多巴胺(DA)。此外,与裸ITO电极相比,ITO-(Ch/NiTsPc)(n)()电极对DA氧化表现出更高的电催化活性。另一方面,只有Ch/FeTsPc和Ch/CuTsPc修饰电极能够区分DA和抗坏血酸。这些结果表明,通过在LbL膜中掺入不同的金属酞菁分子可以制备多功能电极,可用于生物分析应用。