RESUMO
The unique properties of metallic nanostructures of coinage metals that can sustain localized surface plasmon resonances (LSPR) put them at the centre of plasmon-enhanced phenomena. The theory of plasmonic phenomena based on LSPR is well-established. However, the fabrication of plasmonic substrates, reproducibly, is still challenging for applications in surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). In this work we describe well-ordered copper nanostructures (CuNSs), produced by electrodeposition and nanosphere lithography, as active substrates for SEF. After a detailed spectroscopic and microscopic characterization, CuNSs are successfully applied as SEF-active substrates using a well-known perylene derivative as a target molecule. The signal reproducibility from CuNS substrates was established by comparing the results against those obtained from a simply roughened Cu substrate. Under optimal conditions, signal variability is around 4%.
RESUMO
The detection of trace amounts of phenothiazines with fast, direct methods is important for medical applications and the pharmaceutical industry. In this paper we explore the concept of an electronic tongue to detect methylene blue (MB), with a sensor array comprising 6 units. These units were a bare Pt electrode, and Pt electrodes coated with 1-layer LB films of dipalmitoyl phosphatidylcholine (DPPC) and dipalmitoyl phosphatidylglycerol (DPPG), a 5-layer LB film of stearic acid, and 10 nm PVD films of bis benzimidazo perylene (AzoPTCD) and iron phthalocyanine (FePc). The electrical response obtained with impedance spectroscopy varied with the sensing unit, in spite of the small film thickness, thus indicating good cross-sensitivity. Upon treating the capacitance data at 1 kHz with Principal Component Analysis (PCA), the sensor array was capable of distinguishing MB solutions from ultrapure water down to 1 nM. This unprecedented high sensitivity was probably due to strong interactions between MB and DPPC and DPPG, as the sensing units of these phospholipids gave the most important contributions to the PCA plots. Such strong interaction was not manifested in the surface pressure-area isotherms of co-spread monolayers of MB and DPPC or DPPG, which emphasizes the high sensitivity of the electrical measurements in ultrathin films in contact with liquids, now widely exploited in electronic tongues.
Assuntos
Nanopartículas/química , Fenotiazinas/química , 1,2-Dipalmitoilfosfatidilcolina/química , Benzimidazóis/química , Impedância Elétrica , Eletroquímica/métodos , Eletrodos , Compostos Ferrosos/química , Indóis/química , Azul de Metileno/química , Perileno/análogos & derivados , Perileno/química , Fosfatidilgliceróis/química , Fosfolipídeos/química , Platina/química , Análise de Componente Principal , Ácidos Esteáricos/química , Propriedades de SuperfícieRESUMO
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.
RESUMO
Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication ( approximately 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).