RESUMO
The conceptual expansion, fast development, and general acceptance of flow analysis are consequence of its adherence to the principles of green and white analytical chemistry, and chemical derivatization plays an essential role in this context. Through the flow analysis development, however, some of its potentialities and limitations have been overlooked. This is more evident when the involved modifications in flow rates, timing and/or manifold architecture deteriorate the analytical signals. These aspects have not always been systematically investigated, and are addressed here in relation to flow analyzers with UV-Vis spectrophotometric detection. Novel strategies for solution handling, guidance for dealing with the aforementioned analytical signal deterioration, and an alternative possibility for exploiting differential aspiration are presented. The concept of blank reagent carrier stream is proposed.
RESUMO
Chemical derivatization for improving selectivity and/or sensitivity is a common practice in analytical chemistry. It is particularly attractive in flow analysis in view of its highly reproducible reagent addition(s) and controlled timing. Then, measurements without attaining the steady state, kinetic discrimination, exploitation of unstable reagents and/or products, as well as strategies compliant with Green Analytical Chemistry, have been efficiently exploited. Flow-based chemical derivatization has been accomplished by different approaches, most involving flow and manifold programming. Solid-phase reagents, novel strategies for sample insertion and reagent addition, as well as to increase sample residence time have been also exploited. However, the required alterations in flow rates and/or manifold geometry may lead to spurious signals (e.g., Schlieren effect) resulting in distorted peaks and a noisy/drifty baseline. These anomalies can be circumvented by a proper flow system design. In this review, these aspects are critically discussed mostly in relation to spectrophotometric and luminometric detection.