RESUMEN
We demonstrated here that molecular redox films are electrochemical capacitive devices possessing specific field effect in which molecular moieties within films act as sensitive gates. We confirm that the field effect present in these redox switches is suitable in detecting, in a label-free manner (without needs of redox probe in the biological samples), biomarkers of essential importance for dengue, heart risks and inflammation, Parkinson's disease and tumors. Though the sensitiveness is high, it is governed by Thomas Fermi screening and thus depends on the target-to-receptor size ratio. Thus, we also demonstrated how this target-to-receptor size ratio affects the sensitivity. We concluded that the smaller the biological receptor the greater the sensitivity. Consequently, a larger molecular target associated with a smaller receptor provides a considerable (predictable) improvement of the sensitiveness.
Asunto(s)
Biomarcadores/química , Técnicas Biosensibles , Técnicas Electroquímicas , Dengue/diagnóstico , Cardiopatías/diagnóstico , Humanos , Inflamación/diagnóstico , Oxidación-Reducción , Enfermedad de Parkinson/diagnósticoRESUMEN
NS1 is a biomarker for different Flavivirus diseases such as dengue (DENV), zika (ZIKV) and chikungunya (CHIKV) and was herein selectively quantified by electrochemical capacitive sensing (an impedance-derived capacitance methodology wherein the redox probe is contained in the receptive layer) mainly aiming dengue diagnosis in phosphate buffer saline and blood serum environments (up to the neat level). The capacitive sensing was compared to traditional concurrent impedimetric approach (in which the redox probe is added in the biological solution) and other transient methods stated in the literature regarding figures of merit such as limit of detection, linear range, relative standard deviation and affinity constant. Capacitive and impedimetric assays showed equivalent results for linear range, repeatability, sensitivity and constant of affinity. Nonetheless capacitive assays presented better reproducibility with a relative standard deviation (RSD) of 3±1 and 7±4 (all in percentage) in PBS and serum, respectively, meanwhile for impedimetric assays the RSD values were 9±5 in PBS and 12±6 in serum. Thus, by using capacitive assays, an improvement on the analytical performance was observed with the limit of detection about sixty-fold lower in neat serum (â¼0.5ngmL-1 for capacitive over â¼30ngmL-1 for impedimetric assays) compared to traditional electrochemistry methods in general hence demonstrating the superior detection sensitivity for NS1 protein. Accordingly, redox tagged capacitive assays are suitable for the development of multiplex point-of-care neglected diseases sensing applications.
Asunto(s)
Espectroscopía Dieléctrica/métodos , Infecciones por Flavivirus/sangre , Infecciones por Flavivirus/diagnóstico , Flavivirus/aislamiento & purificación , Proteínas no Estructurales Virales/sangre , Técnicas Biosensibles/métodos , Dengue/sangre , Dengue/diagnóstico , Dengue/virología , Virus del Dengue/aislamiento & purificación , Infecciones por Flavivirus/virología , Humanos , Límite de Detección , Reproducibilidad de los Resultados , Proteínas no Estructurales Virales/análisisRESUMEN
The transducer faradaic signals of molecularly receptive interfaces associated with specific target binding can be sensitively monitored by electrochemical impedance and/or capacitance spectroscopies. A comparative evaluation of both impedimetric (associated with charge transfer resistance) and capacitive (associated with faradaic density of states) approaches was undertaken using C-reactive protein (CRP) antigen and antibody interaction as biomolecular binding model. Aiming at constructing redox free (impedimetric) and redox tethered receptive (capacitive) interfaces engineered by self-assembly monolayer, CRP sensitivity and limit of detections were comparatively assessed regarding biosensor capabilities. Binding affinity constant between CRP and anti-CRP interfacial receptor sites were additionally evaluated by the Langmuir adsorption model. Both the impedimetric and capacitive approaches reported similar values of experimental analytical parameters albeit the latter was found to have the advantage of requiring no solution redox reporter thus making it highly suitable for use in multiplexing affinity arrays.