Volpati D, Alessio P, Zanfolim A A, Storti F C, Job A E, Ferreira M, Riul A, Oliveira O N, Constantino C J L
DFQB, FCT, UNESP, CP 467, 19060-900, Presidente Prudente, SP, Brazil.
J Phys Chem B. 2008 Dec 4;112(48):15275-82. doi: 10.1021/jp804159h.
The possibility of generating distinct film properties from the same material is crucial for a number of applications, which can only be achieved by controlling the molecular architecture. In this paper we demonstrate as a proof-of-principle that ultrathin films produced from iron phthalocyanine (FePc) may be used to detect trace amounts of copper ions in water, where advantage was taken of the cross sensitivity of the sensing units that displayed distinct electrical properties. The ultrathin films were fabricated with three methods, namely physical vapor deposition (PVD), Langmuir-Blodgett (LB), and electrostatic layer-by-layer (LbL) techniques, where for the latter tetrasulfonated phthalocyanine was used (FeTsPc). PVD and LB films were more homogeneous than the LbL films at both microscopic and nanoscopic scales, according to results from micro-Raman spectroscopy and atomic force microscopy (AFM), respectively. From FTIR spectroscopy data, these more homogeneous films were found to have FePc molecules oriented preferentially, tilted in relation to the substrate surface, while FeTsPc molecules were isotropically distributed in the LbL films. Impedance spectroscopy measurements with films adsorbed onto interdigitated gold electrodes indicated that the electrical response depends on the type of film-forming method and varies with incorporation of copper ions in aqueous solutions. Using principal component analysis (PCA), we were able to exploit the cross sensitivity of the sensing units and detect copper ions (Cu(2+)) down to 0.2 mg/L, not only in ultrapure water but also in distilled and tap water. This level of sensitivity is sufficient for quality control of water for human consumption, with a fast, low-cost method.
从同一材料生成不同薄膜特性的可能性对于许多应用至关重要,而这只能通过控制分子结构来实现。在本文中,我们作为原理验证表明,由铁酞菁(FePc)制成的超薄膜可用于检测水中痕量的铜离子,其中利用了显示出不同电学特性的传感单元的交叉敏感性。超薄膜通过三种方法制备,即物理气相沉积(PVD)、朗缪尔 - 布洛杰特(LB)和静电逐层(LbL)技术,对于后者使用了四磺化酞菁(FeTsPc)。根据显微拉曼光谱和原子力显微镜(AFM)的结果,PVD和LB薄膜在微观和纳米尺度上比LbL薄膜更均匀。从傅里叶变换红外光谱数据可知,这些更均匀的薄膜中FePc分子优先取向,相对于基底表面倾斜,而FeTsPc分子在LbL薄膜中呈各向同性分布。对吸附在叉指金电极上的薄膜进行阻抗谱测量表明,电响应取决于成膜方法的类型,并随水溶液中铜离子的加入而变化。使用主成分分析(PCA),我们能够利用传感单元的交叉敏感性,不仅在超纯水中,而且在蒸馏水和自来水中检测低至0.2 mg/L的铜离子(Cu(2+))。这种灵敏度水平足以通过一种快速、低成本的方法对供人类消费的水进行质量控制。