RESUMO

Surface-Enhanced Raman Spectra (SERS) of methyl N-(1H-benzimidazol-2-yl)carbamate (MBC), usually named carbendazim, have been recorded on silver colloids at different pH values. In order to identify the neutral, protonated or deprotonated species of MBC that originate the SERS, the vibrational wavenumbers of these three isolated forms and linked to a silver atom have been predicted by carrying out DFT calculations. The results indicate that the active SERS species in the studied pH range correspond to the neutral MBC and its deprotonated ion in the amidate form. According to theoretical calculations, neutral MBC is linked to the metal through the imidazolic nitrogen atom, while the deprotonated MBC could be linked through the imidazolic nitrogen together with the amidic nitrogen atom or the carbonyl oxygen atom. Both adsorbed species, neutral and deprotonated, have the benzimidazolic ring orientated almost perpendicular to the silver surface and no molecular reorientation has been detected. pH of the bulk controls the relative abundance of the neutral MBC and its amidate anion which can be monitored through the intensities of the SERS bands recorded at about 1230 and 1270cm(-1). These two key bands correspond to the in-plane NH deformation of amidic and imidazolic groups, respectively.

RESUMO

Nanostructured films of dioctadecyldimethylammonium bromide (DODAB) and nickel tetrasulfonated phthalocyanine (NiTsPc) were layer-by-layer (LbL) assembled to achieve a synergistic effect considering the distinct properties of both materials. Prior to LbL growth, the effect of NiTsPc on the structure of DODAB vesicles in aqueous medium was investigated by differential scanning calorimetry (DSC). Therefore, DODAB/NiTsPc LbL films were prepared using NiTsPc at concentrations below and above the limit concentration of vesicle formation according to our DSC experiments. As a result, LbL films with distinct nanostructures were obtained, which were studied at micro and nanoscales by micro-Raman and atomic force microscopy, respectively. A linear growth of the LbL films was observed by ultraviolet-visible absorption spectroscopy. However, the bilayer thickness and the surface morphology of the LbL films were radically affected depending on NiTsPc concentration. The electrostatic interaction between DODAB and NiTsPc was identified via Fourier transform infrared (FTIR) absorption spectroscopy as the main driving force responsible for LbL growth. Because LbL films have been widely applied as transducers in sensing devices, DODAB/NiTsPc LbL films having distinct nanostructures were tested as proof-of-principle in preliminary sensing experiments toward dopamine detection using impedance spectroscopy (e-tongue system). The real capacitance vs. dopamine concentration curves were treated using Principal Component Analysis (PCA) and an equivalent electric circuit, revealing the role played by the LbL film nanostructure and the possibility of building calibration curves.

Assuntos

RESUMO

Thin films of cobalt phthalocyanine (CoPc) were deposited onto solid substrates through physical vapor deposition (PVD) by thermal evaporation up to 60 nm thick to determine their molecular architecture and electrical properties. The growth was monitored using UV-Vis absorption spectroscopy, revealing a linear increase for absorbance versus thickness. PVD films were found in the crystalline alpha phase and with the CoPc molecules forming ca. 45 degrees in relation to the substrate surface. The film surface was fairly homogeneous at the micro and nanoscales, with the roughness at ca. 3 nm. DC and AC electrical measurements were carried out for devices built with distinct structures. Perpendicular contact was established by depositing 60 nm CoPc PVD films between indium tin oxide (ITO) and Al, forming a sandwich-type structure (ITO/CoPc/Al). The current versus DC voltage curve indicated a Schottky diode behavior with a rectification factor of 4.2. The AC conductivity at low frequencies increased about 2 orders of magnitude (10(-9) to 10(-7) S/m) with increasing DC bias (0 to 5 V) and the dielectric constant at 1 kHz was 3.45. The parallel contact was obtained by depositing 120 nm CoPc PVD film onto interdigitated electrodes, forming an IDE-structured device. The latter presented a DC conductivity of 5.5 x 10(-10) S/m while the AC conductivity varied from 10(-9) to 10(-1) S/m between 1 Hz and 1 MHz, respectively, presenting no dependence on DC bias. As proof-of-principle, the IDE-structured device was applied as gas sensor for trifluoroacetic acid (TFA).