RESUMEN
Single-drop microextraction (SDME) was coupled with surface-enhanced Raman scattering (SERS) to provide sample extraction and pre-concentration for detection of analyte at low concentrations. A gold nanohole array substrate (AuNHAS), fabricated by interference lithography, was used as SERS substrate and para-mercaptobenzoic acid (p-MBA) was tested as a probe molecule, in the concentration range 10-8-10-4 mol L-1. With this approach, a limit of 10-7 mol L-1 was clearly detected. To improve the detection to lower p-MBA concentration, as 10-8 mol L-1, the SDME technique was applied. The p-MBA Raman signature was detected in two performed extractions and its new concentration was determined to be ~4.6 × 10-5 mol L-1. This work showed that coupling SDME with SERS allowed a rapid (5 min) and efficient pre-concentration (from 10-8 mol L-1 to 10-5 mol L-1), detection, and quantification of the analyte of interest, proving to be an interesting analytical tool for SERS applications.
RESUMEN
Isothermal calorimetry was used to determine enthalpy changes for interaction of divalent cobalt, nickel, copper, and zinc chlorides with silica gel functionalized with vanillin, Sil-Van. The thermal effect, Q(int), and the corresponding amount of cation that interacts, n(int), were obtained in the same experiment. Langmuir expressions for adsorption isotherms were applied to determine the maximum adsorption capacity to form a monolayer, N(mon), and the energy of interaction for a saturated monolayer per gram of Sil-Van, Q(mon). From knowledge of N(mon) and Q(mon), the molar enthalpy of interaction for formation of a monolayer of anchored cations per gram of Sil-Van, Delta(mon)H(m), was determined. Interactions between the Lewis-acidic cations and the donor atom attached to silica are reflected by Delta(mon)Hm values in the order Ni2+ > Cu2+ > Zn2+ congruent with Co2+.