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Carbon-Based Electrode Differential Pulse Voltammetry for Gallic
Acid Quantification in Wine
Johanna Gómez
ABSTRACT: (Word Style “BD_Abstract”). All manuscripts must be accompanied by an abstract. The abstract should briefly state
the problem or purpose of the research, indicate the theoretical or experimental plan used, summarize the principal findings, and
point out the major conclusions.ggfg
Abstract length is one paragraph.
INTRODUCCIÓN
El ácido gálico (GA, Figura 1Error: Reference source not
found) es uno de los principales componentes fenólicos que se
encuentran en el vino. 1 Recientemente, los polifenoles, en
especial los presentes naturalmente en los alimentos han sido
un tema de creciente interés debido a sus propiedades biológi-
cas, incluidas actividades antiinflamatorias, antihistamínicas y
antitumorales, eliminación de radicales libres y protección
contra enfermedades cardiovasculares. 2
El vino es una bebida compleja, es una mezcla de cientos de
compuestos presentes en diferentes concentraciones, con agua,
etanol, glicerol, azúcares y ácidos orgánicos como componen-
tes principales. 3 Con excepción del etanol y el glicerol, otros
alcoholes alifáticos, aminoácidos aromáticos, y los compues-
tos fenólicos están presentes en niveles de concentración mu-
cho más bajos. Además, la concentración de compuestos fenó-
licos en el vino depende de la práctica de vinificación, el clima
y los parásitos del campo, entre otros factores. 4 Debido al
efecto de los antioxidantes fenólicos en la salud humana, es
necesario el desarrollo de métodos robustos y sensibles para su
determinación ha ganado importancia.
La importancia de los compuestos fenólicos ha llevado al
desarrollo de algunos métodos para su determinación en diver-
sos tipos de muestras, entre ellos la quimioluminiscencia 5, la
espectrofotometría 6 y la electroforesis capilar 7, 8, así como la
cromatografía. 9
Se han descrito varios métodos electroquímicos para la
determinación de GA en extractos de plantas y muestras de
alimentos y bebidas. 10, 11 Gunckel et al. 12 investigaron el com-
portamiento electroquímico de GA en una solución acuosa.
Los autores sugirieron que la oxidación se producía mediante
dos pasos de transferencia de electrones con un proceso irre-
versible, controlado por difusión y dependiente del pH, en
específico a pH bajo. Piljac-Zegarac et al. 13 propusieron la
determinación electroquímica de la capacidad antioxidante de
tés de frutas, utilizando un electrodo de carbón vítreo (GCE).
En los últimos tiempos se han propuesto diferentes métodos
electroquímicos para la caracterización de los polifenoles en el
vino basándose en que prácticamente todas las moléculas
polifenólicas presentes en el vino son electroquímicamente
activas. 14 La voltamperometría cíclica (CV) fue el primer
método electroquímico utilizado para la caracterización de

polifenoles y la determinación del contenido total de polifeno-
les (TP) en vinos. 15
La voltamperometría de pulso diferencial (DPV) también se
ha explorado en la detección analítica de polifenoles en ali-
mentos. Así, Blasko et al. 16 utilizaron DPV para la caracteriza-
ción de flavonoides y ácidos fenólicos en jugos de frutas.
El propósito del presente estudio es investigar el comporta-
miento voltamétrico del GA utilizando un electrodo de pasta
de carbono, con el objetivo de desarrollar su determinación
sencilla y rápida a bajos niveles de concentración mediante
voltametría de pulso diferencial (DPV).
Para validar el procedimiento propuesto se realizó la deter-
minación de polifenoles totales en muestra de vino blanco y
los resultados obtenidos se compararon con los protocolos
recomendados.
MATERIALES Y MÉTODOS
Reactivos. Todas las soluciones se prepararon usando agua
destilada. Todos los productos químicos eran de grado reactivo
analítico y se utilizaron sin purificación adicional. En todos los
experimentos se utilizaron soluciones buffer de citrato, 0,1 M
a pH 3, como electrolito de soporte. Ácido gálico monohidra-
tado, ácido cítrico, hidróxido de sodio.
Instrumentos. Las mediciones voltamétricas de pulsos
cíclicos y diferenciales se realizaron con un potenciostato/gal-
vanostato micro AUTO LAB (Ecochemie) controlado por una
computadora personal utilizando el software Nora 2.1. Se
utilizó una celda voltamétrica de vidrio de 100,0 ml de capaci-
dad. El electrodo de trabajo fue la pasta de carbón, electrodo
de referencia de platino y una placa de platino fue el contra-
electrodo.
Voltamogramas de pulsos cíclicos y diferenciales. El
electrodo de pasta de carbón se sometió previamente a voltam-
perometría cíclica en un rango de potenciales entre 0 y 1 V,
utilizando un buffer citrato de 0,1 M a pH 3, con el fin de
asegurar la ausencia de impurezas tanto en el electrodo como
en el buffer (Figura 2Error: Reference source not found).
Posteriormente, para la detección de ácido gálico, se realizó un
voltamograma cíclico (CV) de ácido gálico a una concentra-
ción de 1 × 10-6 mol L-1, en una ventana de potencial de 0 a 1V,
con una velocidad de escaneo de 0.1 V y pH 3, empleando un
buffer de citrato.
Figura 2, Perfil voltamperométrico cíclico de la solución buffer
de citrato de pH 3 con pasta de carbón.
Asimismo, se llevaron a cabo voltamogramas de pulso
diferencial en una ventana de potencial de 0 a 1 V, utilizando
diferentes amplitudes de pulso en el rango de 0.06 a 0.2 V.
Estos experimentos se desarrollaron en soluciones conteniendo
una concentración de 1× 10-6 mol L-1 de ácido gálico.
Preparación de muestras y determinación de ácido gáli-
co. El análisis del ácido gálico en la muestra de vino blanco
mediante el método voltamperométrico propuesto se realizó a
partir de muestras de vino disponibles comercialmente en
España. Los voltamogramas de pulso diferencial se registraron
en el rango de potencial de 0,2 a 0,57 V, utilizando una veloci-
dad de escaneo de 20 mV s-1, un tiempo de modulación de 10
ms y una amplitud de pulso de 0,09 V. El contenido de ácido
gálico en estas muestras fue determinado por el método de
adición estándar.
RESULLTADOS Y DISCUSIÓN
Comportamiento electroquímico del ácido gálico en
electrodos con paso de carbono. La Figura 3 muestra el
voltamograma cíclico típico de 1 x 10-6 mol L-11 GA en una
solución tampón de citrato, pH 3, en un electrodo CPE de
pasta de carbón. El voltamograma cíclico indicó que la oxida-
ción electroquímica de GA estuvo representada por un pico
anódico para todos los electrodos probados. El pico se atribu-
yó a la formación del radical semiquinona y su oxidación a la
forma quinona. Este proceso involucró a un protón y un elec-
trón, sin picos en el barrido inverso, lo que indica un proceso
irreversible. El proceso de oxidación mencionado anterior-
mente se puede atribuir a la ruta bien descrita para la oxida-
ción de fenoles, hidroquinonas y derivados,23 como se mues-
tra en el Esquema 1. En la Figura 3, utilizando un CPE, se
observó que este pico se desplazó a 0,46.
Figura 3, Perfil voltamperométrico cíclico resultante de la oxida-
ción electroquímica de 1,0 × 10-6 mol L-1 de ácido gálico en un
buffer de citrato de pH 3 con pasta de carbón.

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 1.6

1.4

1.2
Corriente (μA)

0.8

0.6

0.4

0.2

0
0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55

E (V)
0.8 0.9 0.1 0.06

Figura 4, Voltamogramas de pulso diferencial obtenidos utilizan-

do diferentes valores de amplitud de pulso.

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